KR101628211B1 - Method for manufacturing semiconductor device, substrate processing method, substrate processing apparatus, and recording medium - Google Patents

Abstract

A step of supplying a first source gas containing a predetermined element and a halogen group to a substrate in the treatment chamber and a step of supplying a second source gas containing a predetermined element and an amino group to the substrate in the treatment chamber are alternately performed a predetermined number of times , A step of forming a first layer containing a predetermined element, nitrogen and carbon on the substrate; The pressure in the process chamber is made larger than the pressure in the process chamber when the first source gas, the second source gas and the reaction gas are supplied, and the amine source gas containing carbon, nitrogen and hydrogen is supplied to the substrate in the process chamber, Modifying the layer to form a second layer; And a step of forming a third layer by modifying the second layer by supplying a reaction gas different from each of the source gases to the substrate in the treatment chamber by performing a predetermined number of times, A thin film of a predetermined composition is formed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a semiconductor device manufacturing method, a substrate processing method, a substrate processing apparatus,

The present invention relates to a semiconductor device manufacturing method, a substrate processing method, a substrate processing apparatus, and a recording medium including a step of forming a thin film on a substrate.

The requirements for a low-temperature film, a low dielectric constant, and a low HF wet etching rate are increasing for a thin film such as an insulating film constituting the side wall spacer (SWS) of the gate electrode or the like along with miniaturization of the transistor. A silicon carbonitride film (SiCN film) in which carbon (C) is added to a silicon nitride film (SiN film) or a silicon oxynitride film (SiOCN film) in which oxygen (O) is added is used as an insulating film . Since these insulating films are required to have high step coverage characteristics, they are often formed by an alternate feeding method in which processing gases are alternately supplied (see, for example, Patent Document 1).

1. Japanese Patent Laid-Open Publication No. 2011-192875

In order to further improve the resistance to hydrofluoric acid (HF) or decrease the dielectric constant of the insulating film such as the above-mentioned SiCN film or SiOCN film, it is necessary to decrease the nitrogen concentration in the film, increase the carbon concentration, or increase the oxygen concentration Valid. However, it has not been easy to form a thin film which can have a carbon concentration exceeding the nitrogen concentration, for example, by the conventional alternate feeding method. Also, it is not easy to appropriately control the carbon concentration and the nitrogen concentration in the thin film. When forming the insulating film constituting the sidewall spacer or the like, it is required to lower the film forming temperature. However, the film forming temperature in the conventional alternate feeding method is about 600 占 폚. In the low temperature region of, for example, 550 占 폚 or less, Was not easy to form.

Accordingly, an object of the present invention is to provide a method of manufacturing a semiconductor device, a substrate processing method, a substrate processing apparatus, and a recording medium, which can form a high-quality thin film by controlling the composition of the film in a low temperature region.

According to one aspect of the present invention,

A step of supplying a first raw material gas containing a predetermined element and a halogen group to a substrate in a treatment chamber and a step of supplying a second raw material gas containing the predetermined element and an amino group to the substrate in the treatment chamber, Forming a first layer containing the predetermined element, nitrogen and carbon on the substrate by performing a predetermined number of times with the first element and the second element;

The pressure in the processing chamber is made larger than the pressure in the processing chamber when the first source gas, the second source gas, and the reaction gas are supplied, and an amine source gas containing carbon, nitrogen, and hydrogen is introduced into the processing chamber The first layer is modified to form a second layer containing a higher proportion of nitrogen than the proportion of nitrogen contained in the first layer and a higher proportion of carbon than the proportion of carbon contained in the first layer ; And

Forming a third layer by reforming the second layer by supplying the reaction gas different from the respective source gases to the substrate in the treatment chamber;

A step of forming a thin film of a predetermined composition including the predetermined element on the substrate by performing a cycle a predetermined number of times.

According to another aspect of the present invention,

A step of supplying a first source gas containing a predetermined element and a halogen group to a substrate in a treatment chamber and a step of supplying a second source gas containing the predetermined element and an amino group to the substrate in the treatment chamber are alternately performed a predetermined number of times Thereby forming a first layer containing the predetermined element, nitrogen and carbon on the substrate;

The pressure in the processing chamber is made larger than the pressure in the processing chamber when the first source gas, the second source gas, and the reaction gas are supplied, and an amine source gas containing carbon, nitrogen, and hydrogen is introduced into the processing chamber The first layer is modified to form a second layer containing a higher proportion of nitrogen than the proportion of nitrogen contained in the first layer and a higher proportion of carbon than the proportion of carbon contained in the first layer ; And

Forming a third layer by reforming the second layer by supplying the reaction gas different from the respective source gases to the substrate in the treatment chamber;

A step of forming a thin film of a predetermined composition including the predetermined element on the substrate by performing a cycle a predetermined number of times.

According to another aspect of the present invention,

A processing chamber for accommodating a substrate;

A first raw material gas supply system for supplying a first raw material gas containing a predetermined element and a halogen group to the substrate in the treatment chamber;

A second source gas supply system for supplying a second source gas containing the predetermined element and the amino group to the substrate in the treatment chamber;

A third source gas supply system for supplying an amine-based source gas containing carbon, nitrogen and hydrogen to the substrate in the treatment chamber;

A reaction gas supply system for supplying a reaction gas different from the respective source gases to the substrate in the processing chamber; And

A process for supplying the first source gas to the substrate in the process chamber and a process for supplying the second source gas to the substrate in the process chamber are alternately performed a predetermined number of times to form the predetermined element, And forming a first layer containing carbon on the surface of the substrate in the process chamber; and a process of forming a first layer containing carbon and a pressure in the process chamber, wherein the pressure in the process chamber is larger than the pressure in the process chamber when supplying the first source gas, the second source gas, The first layer is modified to supply the amine-based source gas to a portion of the first layer in which the ratio of nitrogen to nitrogen contained in the first layer is higher than that of nitrogen contained in the first layer, Forming a second layer including the second layer on the substrate, and supplying the reaction gas to the substrate in the processing chamber to modify the second layer And forming a thin film of a predetermined composition including the predetermined element on the substrate by performing a cycle including a process of forming a third layer by a predetermined number of times, A control unit for controlling the supply system, the third source gas supply system, and the reaction gas supply system;

And a substrate processing apparatus.

According to another aspect of the present invention,

A step of supplying a first raw material gas containing a predetermined element and a halogen group to a substrate in a processing chamber of the substrate processing apparatus and a step of supplying a second raw material gas containing the predetermined element and an amino group to the substrate in the processing chamber, A step of forming a first layer containing the predetermined element, nitrogen and carbon on the substrate by performing a predetermined number of times;

The pressure in the processing chamber is made larger than the pressure in the processing chamber when the first source gas, the second source gas, and the reaction gas are supplied, and an amine source gas containing carbon, nitrogen, and hydrogen is introduced into the processing chamber The first layer is modified to form a second layer containing a higher proportion of nitrogen than the proportion of nitrogen contained in the first layer and a higher proportion of carbon than the proportion of carbon contained in the first layer Order; And

Forming a third layer by reforming the second layer by supplying the reaction gas different from the respective source gases to the substrate in the treatment chamber;

There is provided a computer-readable recording medium recording a program that causes a computer to execute a procedure of forming a thin film of a predetermined composition including the predetermined element on a substrate by performing a cycle a predetermined number of times.

According to the present invention, it is possible to provide a semiconductor device manufacturing method, a substrate processing method, a substrate processing apparatus, and a recording medium, which can form a high quality thin film by controlling the film composition in a low temperature region.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic configuration diagram of a vertical type processing of a substrate processing apparatus preferably used in the present embodiment, and showing a processing furnace portion in a cross-sectional view. Fig.
Fig. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in the present embodiment, and shows a processing furnace portion as a sectional view taken along line AA of Fig.
3 is a schematic configuration view of a controller of a substrate processing apparatus preferably used in the present embodiment.
4 is a diagram showing an example of the film formation flow in the first sequence of this embodiment.
5 is a diagram showing an example of the film formation flow in the second sequence of the present embodiment.
6 is a diagram showing an example of the film formation flow in the third sequence of the present embodiment.
7 is a diagram showing an example of timing of gas supply in the first sequence of the present embodiment;
8 is a diagram showing an example of timing of gas supply in the second sequence of the present embodiment;
Fig. 9 is a diagram showing an example of the timing of gas supply in the third sequence of the present embodiment. Fig. 9 (a) shows a sequence example in which film formation is performed without using plasma , And FIG. 9 (b) is a diagram showing a sequence example in which film formation is performed using plasma.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings.

Fig. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in the present embodiment, and shows a part of the processing furnace 202 as a longitudinal sectional view. 2 is a schematic configuration diagram of a vertical treatment furnace preferably used in the present embodiment, and a portion of the treatment furnace 202 is shown by a cross-sectional view along line A-A in Fig. Further, the present invention is not limited to the substrate processing apparatus according to the present embodiment, but can be suitably applied to a substrate processing apparatus including a single row type, a hot wall type, and a cold wall type processing furnace.

As shown in Fig. 1, the processing furnace 202 includes a heater 207 as a heating means (heating mechanism). The heater 207 has a cylindrical shape and is vertically installed by being supported by a heater base (not shown) as a holding plate. The heater 207 also functions as an activation mechanism (excitation portion) for activating (exciting) the gas by heat as described later.

A reaction tube 203 constituting a reaction vessel (processing vessel) is disposed (arranged) inside the heater 207 concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC), and is formed into a cylindrical shape in which the upper end is closed and the lower end is opened. A processing chamber 201 is formed in the hollow tube of the reaction tube 203 and the wafer 200 as a substrate is accommodated in a state of being vertically aligned in multiple stages in a horizontal posture by a boat 217, Lt; / RTI >

A first nozzle 249a, a second nozzle 249b, a third nozzle 249c and a fourth nozzle 249d are installed in the treatment chamber 201 so as to pass through the lower portion of the reaction tube 203. The first gas supply pipe 232a, the second gas supply pipe 232b and the third gas supply pipe 232c (not shown) are connected to the first nozzle 249a, the second nozzle 249b, the third nozzle 249c and the fourth nozzle 249d. And the fourth gas supply pipe 232d are respectively connected. And the fifth gas supply pipe 232j is connected to the fourth gas supply pipe 232d. In this way, the reaction tube 203 is provided with four nozzles 249a, 249b, 249c and 249d and five gas supply pipes 232a, 232b, 232c, 232d and 232j, Type gas.

Further, a metal manifold for supporting the reaction tube 203 may be provided below the reaction tube 203, and each nozzle may be provided so as to pass through the side wall of the metal-made manifold. In this case, an exhaust pipe 231, which will be described later, may be further provided on the metal-made manifold. Also in this case, the exhaust pipe 231 may be provided below the reaction tube 203 instead of the metal manifold. As described above, the furnace mouth portion of the processing furnace 202 may be made of metal, and a nozzle or the like may be provided in the furnace portion of the metal furnace.

The first gas supply pipe 232a is provided with a mass flow controller 241a (MFC), which is a flow controller (flow control unit), and a valve 243a, which is an open / close valve, in this order from the upstream side. A first inert gas supply pipe 232e is connected to the first gas supply pipe 232a downstream of the valve 243a. The first inert gas supply pipe 232e is provided with a mass flow controller 241e as a flow controller (flow control unit) and a valve 243e as an open / close valve in this order from the upstream side. The first nozzle 249a described above is connected to the distal end of the first gas supply pipe 232a. The first nozzle 249a is disposed in a circular arc space between the inner wall of the reaction tube 203 and the wafer 200 from the lower portion to the upper portion of the inner wall of the reaction tube 203 toward the upper side of the loading direction of the wafer 200 Is set up to rise. That is, the first nozzle 249a is installed along the wafer arrangement area in a region horizontally surrounding the wafer arrangement area on the side of the wafer arrangement area where the wafer 200 is arranged. The first nozzle 249a is configured as an L-shaped long nozzle, and the horizontal portion thereof is provided so as to pass through the lower side wall of the reaction tube 203. The vertical portion of the first nozzle 249a extends from one end side (one end side) (The other end side). A gas supply hole 250a for supplying a gas is provided on the side surface of the first nozzle 249a. The gas supply hole 250a is opened so as to face the center of the reaction tube 203 and is capable of supplying gas toward the wafer 200. [ A plurality of the gas supply holes 250a are provided from the lower portion to the upper portion of the reaction tube 203, each having the same opening area and the same opening pitch.

The first gas supply system is constituted mainly by the first gas supply pipe 232a, the mass flow controller 241a and the valve 243a. Also, the first nozzle 249a may be included in the first gas supply system. The first inert gas supply system is mainly constituted by the first inert gas supply pipe 232e, the mass flow controller 241e and the valve 243e. The first inert gas supply system also functions as a purge gas supply system.

The second gas supply pipe 232b is provided with a mass flow controller 241b (MFC), which is a flow controller (flow control unit), and a valve 243b, which is an open / close valve, in this order from the upstream side. A second inert gas supply pipe 232f is connected to the second gas supply pipe 232b on the downstream side of the valve 243b. A mass flow controller 241f, which is a flow controller (flow control unit), and a valve 243f, which is an open / close valve, are provided in this second inert gas supply pipe 232f in this order from the upstream side. The second nozzle 249b is connected to the tip of the second gas supply pipe 232b. The second nozzle 249b is disposed in a circular arc space between the inner wall of the reaction tube 203 and the wafer 200 from the lower portion to the upper portion of the inner wall of the reaction tube 203 toward the upper side of the stacking direction of the wafer 200 . Namely, the second nozzle 249b is installed along the wafer arrangement region in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region in which the wafer 200 is arranged. The second nozzle 249b is configured as an L-shaped long nozzle, and the horizontal portion thereof is provided so as to pass through the lower side wall of the reaction tube 203, and the vertical portion of the second nozzle 249b is moved upward at least from the one end side to the other end side Respectively. A gas supply hole 250b for supplying a gas to the side surface of the second nozzle 249b is provided. The gas supply hole 250b is opened so as to face the center of the reaction tube 203 and is capable of supplying gas toward the wafer 200. A plurality of the gas supply holes 250b are provided from the lower portion to the upper portion of the reaction tube 203, each having the same opening area and the same opening pitch.

The second gas supply system is constituted mainly by the second gas supply pipe 232b, the mass flow controller 241b and the valve 243b. Further, the second nozzle 249b may be included in the second gas supply system. The second inert gas supply system is mainly constituted by the second inert gas supply pipe 232f, the mass flow controller 241f and the valve 243f. The second inert gas supply system also functions as a purge gas supply system.

A mass flow controller 241c (MFC), which is a flow rate controller (flow control unit), and a valve 243c, which is an opening / closing valve, are provided in this order from the upstream side in the third gas supply pipe 232c. A third inert gas supply pipe 232g is connected to the third gas supply pipe 232c on the downstream side of the valve 243c. A mass flow controller 241g, which is a flow controller (flow control unit), and a valve 243g, which is an on / off valve, are provided in this third inert gas supply pipe 232g in this order from the upstream side. The third nozzle 249c is connected to the tip of the third gas supply pipe 232c. The third nozzle 249c is disposed in a circular arc space between the inner wall of the reaction tube 203 and the wafer 200 from the lower portion to the upper portion of the inner wall of the reaction tube 203 toward the upper side of the loading direction of the wafer 200 . That is, the third nozzle 249c is installed along the wafer arrangement region in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region in which the wafer 200 is arranged. The third nozzle 249c is configured as an L-shaped long nozzle, and the horizontal portion thereof is provided so as to pass through the lower side wall of the reaction tube 203, and the vertical portion of the third nozzle 249c is moved upward at least from the one end side to the other end side Respectively. A gas supply hole 250c for supplying gas is provided on the side surface of the third nozzle 249c. The gas supply hole 250c is opened so as to face the center of the reaction tube 203 and is capable of supplying gas toward the wafer 200. [ A plurality of the gas supply holes 250c are provided from the lower part to the upper part of the reaction tube 203, and they have the same opening area and are provided at the same opening pitch.

A third gas supply system is constituted mainly by the third gas supply pipe 232c, the mass flow controller 241c and the valve 243c. The third nozzle 249c may be included in the third gas supply system. Also, a third inert gas supply system is constituted mainly by the third inert gas supply pipe 232g, the mass flow controller 241g, and the valve 243g. The third inert gas supply system also functions as a purge gas supply system.

A mass flow controller 241d (MFC), which is a flow controller (flow control unit), and a valve 243d, which is an opening / closing valve, are provided in this order from the upstream side in the fourth gas supply pipe 232d. The fifth gas supply pipe 232j is connected to the downstream side of the valve 243d of the fourth gas supply pipe 232d. The fifth gas supply pipe 232j is provided with a mass flow controller 241j, which is a flow controller (flow control unit), and a valve 243j, which is an open / close valve, in this order from the upstream side. The fourth inert gas supply pipe 232h is connected to the fourth gas supply pipe 232d on the downstream side of the connection point with the fifth gas supply pipe 232j. A mass flow controller 241h, which is a flow controller (flow control unit), and a valve 243h, which is an on-off valve, are provided in this fourth inert gas supply pipe 232h in this order from the upstream side. The fourth nozzle 249d is connected to the tip of the fourth gas supply pipe 232d. The fourth nozzle 249d is installed in the buffer chamber 237 which is a gas dispersion space.

The buffer chamber 237 is provided in a circular arc space between the inner wall of the reaction tube 203 and the wafer 200 along the loading direction of the wafer 200 at a portion extending from the lower portion to the upper portion of the inner wall of the reaction tube 203 do. That is, the buffer chamber 237 is provided so as to follow the wafer arrangement region in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region. A gas supply hole 250e for supplying gas to the end of the wall adjacent to the wafer 200 of the buffer chamber 237 is provided. The gas supply hole 250e is opened so as to face the center of the reaction tube 203 and is made capable of supplying gas toward the wafer 200. [ A plurality of gas supply holes 250e are provided from the lower portion to the upper portion of the reaction tube 203, each having the same opening area and the same opening pitch.

The fourth nozzle 249d is disposed at an end opposite to the end where the gas supply hole 250e of the buffer chamber 237 is provided from the lower portion of the inner wall of the reaction tube 203 toward the upper side of the loading direction of the wafer 200 . Namely, the fourth nozzle 249d is installed so as to follow the wafer arrangement area in the area horizontally surrounding the wafer arrangement area on the side of the wafer arrangement area. The fourth nozzle 249d is configured as an L-shaped long nozzle, and the horizontal portion thereof is provided so as to penetrate through the lower side wall of the reaction tube 203, and the vertical portion of the fourth nozzle 249d is moved upward from the one end side to the other end side Respectively. A gas supply hole 250d for supplying gas is provided on the side surface of the fourth nozzle 249d. The gas supply hole 250d is opened toward the center of the buffer chamber 237. [ A plurality of gas supply holes 250d are provided from the lower portion to the upper portion of the reaction tube 203 like the gas supply holes 250e of the buffer chamber 237. The opening areas of the plurality of gas supply holes 250d are equal to each other from the upstream side (lower portion) to the downstream portion (upper portion) when the differential pressure within the buffer chamber 237 and the processing chamber 201 is small However, when the differential pressure is large, it is sufficient to increase the opening area and decrease the opening pitch from the upstream side to the downstream side.

In the present embodiment, the opening areas and the opening pitches of the gas supply holes 250d of the fourth nozzle 249d are adjusted from the upstream side to the downstream side, as described above, The flow rate is about the same, but the flow rate is about the same. The gas ejected from each of the gas supply holes 250d is once introduced into the buffer chamber 237 and the gas flow rate difference in the buffer chamber 237 is equalized.

That is, the gas ejected from each of the gas supply holes 250d of the fourth nozzle 249d into the buffer chamber 237 is supplied to the buffer chamber 237 after the particle velocity of each gas in the buffer chamber 237 is relaxed. And is injected into the processing chamber 201 from the gas supply hole 250e. The gas ejected from each of the gas supply holes 250d of the fourth nozzle 249d into the buffer chamber 237 is ejected from each of the gas supply holes 250e of the buffer chamber 237 into the processing chamber 201 It becomes a gas having a uniform flow rate and flow rate.

A fourth gas supply system is constituted mainly by the fourth gas supply pipe 232d, the mass flow controller 241d and the valve 243d. Further, the fourth nozzle 249d and the buffer chamber 237 may be included in the fourth gas supply system. The fifth gas supply system is mainly constituted by the fifth gas supply pipe 232j, the mass flow controller 241j and the valve 243j. The fourth nozzle 249d and the buffer chamber 237 may be included in the fifth gas supply system. The fourth inert gas supply system is mainly constituted by the fourth inert gas supply pipe 232h, the mass flow controller 241h and the valve 243h. The fourth inert gas supply system also functions as a purge gas supply system.

As described above, the gas supply method in the present embodiment is characterized in that the inner wall of the reaction tube 203 and the nozzles 249a and 249b (hereinafter, referred to as " 249c and 249d and the buffer chamber 237 and the gas supply holes 250a, 250b, 250c and 250d (250a, 250b, 250c and 250d) respectively opened in the nozzles 249a, 249b, 249c and 249d and the buffer chamber 237, And 250e in the vicinity of the wafer 200 so that the main flow of gas in the reaction tube 203 is directed in a direction parallel to the surface of the wafer 200, . With this configuration, gas can be uniformly supplied to each wafer 200, and the film thickness of the thin film formed on each wafer 200 can be made uniform. Although the residual gas after the reaction flows toward the exhaust port, that is, the exhaust pipe 231 described later, the direction in which the residual gas flows is properly specified by the position of the exhaust port, and is not limited to the vertical direction.

From the first gas supply pipe 232a, a first raw material containing a predetermined element and a halogen group, that is, a first raw material gas containing a silicon (Si) element and a chloro group, for example, as a first silicon raw material gas The chlorosilane-based source gas is supplied into the processing chamber 201 via the mass flow controller 241a, the valve 243a, and the first nozzle 249a. Here, the chlorosilane-based source gas is a gas obtained by vaporizing a chlorosilane-based raw material in a liquid state under ordinary temperature and normal pressure. The chlorosilane-based raw material is a silane-based raw material containing a chloro group and is a raw material containing at least silicon (Si) and chlorine (Cl). That is, the chlorosilane-based raw material referred to herein may be referred to as a kind of halide. In the present specification, when the word "raw material" is used, the term "liquid raw material liquid" means "raw material gas vaporizing the liquid raw material" or both of them . Therefore, when the word " chlorosilane-based raw material " is used in this specification, the term " chlorosilane raw material liquid " means " chlorosilane raw material gas " have. As the chlorosilane-based source gas, for example, hexachlorodisilane (Si ₂ Cl ₆ , abbreviation: HCDS) gas can be used. When a liquid raw material in a liquid state is used at room temperature and atmospheric pressure, such as HCDS, a liquid raw material is vaporized by a vaporization system such as a vaporizer or a bubbler, and is supplied as a raw material gas (HCDS gas).

A second raw material containing a predetermined element and an amino group (amine group), that is, a silicon compound containing a silicon (Si) element and an amino group as a second silicon source gas (second silicon containing gas) 2 is supplied into the processing chamber 201 via the mass flow controller 241b, the valve 243b, and the second nozzle 249b. Here, the aminosilane-based source gas is a gas obtained by vaporizing an aminosilane-based raw material in a liquid state under ordinary temperature and normal pressure. The aminosilane-based raw material is a silane-based raw material (also a silane-based raw material containing an alkyl group such as a methyl group, an ethyl group or a butyl group) containing an amino group and at least silicon (Si), nitrogen (N) It is the raw material involved. That is, the aminosilane-based raw material referred to herein may be referred to as an organic-based raw material and may be referred to as an organic aminosilane-based raw material. When the word "aminosilane-based raw material" is used in the present specification, the term "aminosilane raw material in a liquid state" means the case of "aminosilane raw material gas", or both cases have. As the aminosilane-based source gas, for example, trisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₃ H, abbreviation: 3DMAS) gas can be used. When a liquid raw material in a liquid state is used at room temperature and normal pressure, such as 3DMAS, the liquid raw material is vaporized by a vaporization system such as a vaporizer or a bubbler, and is supplied as a raw material gas (3DMAS gas).

From the third gas supply pipe 232c, an amine, that is, an amine-based source gas is supplied into the process chamber 201 via the mass flow controller 241c, the valve 243c, and the third nozzle 249c. Here, the amine-based source gas is a source gas containing an amine group such as an amine-vaporized gas, and is a source gas containing at least carbon (C), nitrogen (N), and hydrogen (H). The amine-based source gas includes amines such as ethylamine, methylamine, propylamine, isopropylamine, butylamine, and isobutylamine. Herein, amine is a generic term for compounds in which hydrogen atoms of ammonia (NH ₃ ) are substituted with hydrocarbon groups such as alkyl groups. That is, the amine includes a hydrocarbon group such as an alkyl group. Since the amine-based source gas does not contain silicon (Si), it may be referred to as a gas containing no silicon, and may also be referred to as a gas containing no silicon or metal, since it does not contain silicon and metal. In addition, the amine-based source gas is a nitrogen-containing gas, a carbon-containing gas, and also a hydrogen-containing gas. The amine-based source gas may also be referred to as a material composed of only the three elements of carbon element (C), nitrogen element (N) and hydrogen element (H). When the word "amine-based raw material" is used in the present specification, the term "amine-based raw material" means "amine-based raw material gas" or both of them. As the amine-based source gas, for example, triethylamine [(C ₂ H ₅ ) ₃ N, abbreviation: TEA] gas can be used. In the case of using a liquid raw material in a liquid state under ordinary temperature and normal pressure conditions such as TEA, the liquid raw material is vaporized by a vaporization system such as a vaporizer or a bubbler and is supplied as a raw material gas (TEA gas).

A gas (nitrogen-containing gas) containing, for example, nitrogen (N) as a nitrification gas is supplied from the fourth gas supply pipe 232d to the mass flow controller 241d, the valve 243d, the fourth nozzle 249d, (Not shown). As the nitrogen-containing gas, for example, ammonia (NH ₃ ) gas can be used.

A gas (oxygen-containing gas) containing, for example, oxygen (O) as an oxidizing gas is supplied from the fifth gas supply pipe 232j to the mass flow controller 241j, the valve 243j, the fourth gas supply pipe 232d, Is supplied into the processing chamber 201 via the buffer chamber 239 and the buffer chamber 237, As the oxygen-containing gas, for example, oxygen (O ₂ ) gas can be used.

An inert gas supply pipe, for example nitrogen from (232e, 232f, 232g, 232h ) (N 2) controllers each gas mass flow (241e, 241f, 241g, 241h ), the valve (243e, 243f, 243g, 243h ), the gas supply tube ( 232a, 232b, 232c, and 232d, gas nozzles 249a, 249b, 249c, and 249d, and a buffer chamber 237. [

Further, in the case where, for example, the above-described gas is flowed from each gas supply pipe, a first silicon source gas supply system as a first source gas supply system for supplying a first source gas containing a predetermined element and a halogen group by a first gas supply system , That is, a chlorosilane-based source gas supply system is constituted. The chlorosilane-based feed gas supply system is also simply referred to as a chlorosilane-based feed supply system. And a second silicon source gas supply system, that is, an aminosilane-based source gas supply system, as a second source gas supply system for supplying a second source gas containing a predetermined element and an amino group by the second gas supply system. The aminosilane-based feed gas supply system is also referred to simply as an aminosilane-based feed system. The third gas supply system constitutes an amine supply system, that is, an amine-based source gas supply system, as a third source gas supply system for supplying the amine-based source gas. The amine-based feed gas supply system is also referred to simply as an amine-based feed system. The fourth gas supply system constitutes a nitrogen-containing gas supply system as a nitrification gas supply system. The fifth gas supply system constitutes an oxygen-containing gas supply system as an oxidizing gas supply system.

When the chlorosilane-based source gas, the aminosilane-based source gas and the amine-based source gas are collectively referred to as a source gas, the chlorosilane-based source gas supply system, the aminosilane-based source gas supply system, and the amine- A raw material gas supply system is constituted. The raw material gas supply system is also simply referred to as a raw material supply system. When a nitrogen-containing gas (nitriding gas) and an oxygen-containing gas (oxidizing gas) are collectively referred to as a reactive gas, a reaction gas supply system is constituted by a nitrogen-containing gas supply system and an oxygen-containing gas supply system. Further, as described above, the amine-based source gas is also referred to as a reactive gas because it is a nitrogen-containing gas, a carbon-containing gas, or a hydrogen-containing gas.

In the buffer chamber 237, a first rod-shaped electrode 269 and a second rod-shaped electrode 270, which are a first electrode having an elongated structure as shown in Fig. 2, Along the direction in which the wafers 200 are stacked. Each of the first rod-shaped electrode 269 and the second rod-shaped electrode 270 is installed in parallel with the fourth nozzle 249d. Each of the first bar-shaped electrode 269 and the second bar-shaped electrode 270 is protected by being covered by an electrode protection tube 275 which is a protection tube protecting each electrode from top to bottom. Either one of the first rod-shaped electrode 269 or the second rod-shaped electrode 270 is connected to the high-frequency power source 273 via the matching unit 272 and the other is connected to the reference potential Earth. Frequency power is applied between the first bar-shaped electrode 269 and the second bar-shaped electrode 270 from the high-frequency power source 273 via the matching unit 272, whereby the first bar-shaped electrode 269 and the second bar- Plasma is generated in the plasma generation region 224 between the two-rod electrodes 270. A plasma source as a plasma generator (plasma generating portion) is constituted mainly by the first rod-like electrode 269, the second rod-shaped electrode 270, and the electrode protecting tube 275. Also, the matcher 272 and the high-frequency power source 273 may be included in the plasma source. The plasma source also functions as an activation mechanism (excitation portion) for activating (exciting) the gas with plasma as described later.

The electrode protection tube 275 has a structure in which each of the first rod-shaped electrode 269 and the second rod-shaped electrode 270 can be inserted into the buffer chamber 237 while being isolated from the atmosphere of the buffer chamber 237 . When the oxygen concentration inside the electrode protection tube 275 is equal to the oxygen concentration in the outside air (atmospheric air), the first rod-like electrode 269 and the second rod- The two-rod electrode 270 is oxidized to heat by the heater 207. Therefore, an inert gas such as nitrogen gas is preliminarily charged into the electrode protection tube 275, or the inside of the electrode protection tube 275 is purged with an inert gas such as nitrogen gas using an inert gas purge mechanism, So that the oxygen concentration inside the first rod-like electrode 279 and the second rod-shaped electrode 270 can be reduced to prevent oxidation of the first rod-shaped electrode 269 or the second rod-shaped electrode 270.

The reaction tube 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. The exhaust pipe 231 is provided with a pressure sensor 245 as a pressure detector (pressure detecting portion) for detecting the pressure in the process chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator A vacuum pump 246 is connected. Further, the APC valve 244 can perform vacuum exhaust and vacuum exhaust stop in the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operated, and furthermore, by operating the vacuum pump 246 A valve configured to adjust the pressure in the process chamber 201 by adjusting the opening degree of the valve in the process chamber 201. [ An exhaust system is mainly composed of an exhaust pipe 231, an APC valve 244, and a pressure sensor 245. The vacuum pump 246 may be included in the exhaust system. The exhaust system controls the opening degree of the valve of the APC valve 244 based on the pressure information detected by the pressure sensor 245 while operating the vacuum pump 246 so that the pressure in the processing chamber 201 is maintained at a predetermined pressure ). ≪ / RTI >

Below the reaction tube 203, a seal cap 219 is provided as a lid body capable of hermetically closing the lower end opening of the reaction tube 203. The seal cap 219 is configured to be in contact with the lower end of the reaction tube 203 from the lower side in the vertical direction. The seal cap 219 is made of metal such as stainless steel and formed into a disc shape. On the upper surface of the seal cap 219, there is provided an O-ring 220 as a seal member which contacts the lower end of the reaction tube 203. On the opposite side of the seal chamber 219 from the process chamber 201, a rotation mechanism 267 for rotating a boat 217 as a substrate support, which will be described later, is provided. The rotating shaft 255 of the rotating mechanism 267 penetrates the seal cap 219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be vertically elevated and lowered by a boat elevator 115 as a vertically installed elevating mechanism on the outside of the reaction tube 203. The boat elevator 115 is constructed so that the boat 217 can be carried in and out of the processing chamber 201 by moving the seal cap 219 up and down. In other words, the boat elevator 115 is configured as a boat 217, that is, as a transfer device (transfer mechanism) for transferring the wafer 200 into and out of the process chamber 201.

The boat 217 as a substrate support is made of a heat-resistant material such as quartz or silicon carbide, and is configured to support a plurality of wafers 200 in a horizontal posture and in a state of being centered to each other and to be supported in multiple stages. A heat insulating member 218 made of a heat resistant material such as quartz or silicon carbide is provided under the boat 217 to prevent heat from the heater 207 from being transmitted to the seal cap 219 side. The heat insulating member 218 may be composed of a plurality of heat insulating plates made of a heat resistant material such as quartz or silicon carbide and a heat insulating plate holder for supporting the heat insulating plates in a horizontal position in multiple stages.

A temperature sensor 263 as a temperature detector is provided in the reaction tube 203 and the state of the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, The temperature is configured to be a desired temperature distribution. Like the nozzles 249a, 249b, 249c, and 249d, the temperature sensor 263 is formed in an L shape and is disposed along the inner wall of the reaction tube 203. [

3, the controller 121 which is a control unit (control means) includes a CPU 121a (Central Processing Unit), a RAM 121b (Random Access Memory), a storage device 121c, an I / O port 121d As shown in Fig. The RAM 121b, the storage device 121c and the I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. The controller 121 is connected to an input / output device 122 configured as, for example, a touch panel.

The storage device 121c is composed of, for example, a flash memory, a hard disk drive (HDD), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe describing the order and condition of substrate processing to be described later, and the like are stored so as to be readable. The process recipe is combined with the controller 121 so as to obtain a predetermined result by executing the respective steps in the substrate processing step to be described later, and functions as a program. Hereinafter, the process recipe, the control program, and the like are collectively referred to simply as a program. In the present specification, the word "program" includes only a process recipe group, or includes only a control program group, or both. Further, the RAM 121b is configured as a memory area (work area) in which programs and data read by the CPU 121a are temporarily held.

The I / O port 121d is connected to the mass flow controllers 241a, 241b, 241c, 241d, 241e, 241f, 241g, 241h, 241j, 243a, 243b, 243c, 243d, 243e, 243f, 243g, 243h 243j, a pressure sensor 245, an APC valve 244, a vacuum pump 246, a heater 207, a temperature sensor 263, a rotation mechanism 267, a boat elevator 115, a high frequency power source 273, Matching device 272, and the like.

The CPU 121a is configured to read and execute the control program from the storage device 121c and to read the process recipe from the storage device 121c in response to an input of an operation command from the input / output device 122. [ The CPU 121a performs various gas flow rate adjustment operations by the mass flow controllers 241a, 241b, 241c, 241d, 241e, 241f, 241g, 241h, and 241j to control the contents of the read process recipe, Closing operation of the APC valve 244 and pressure adjusting operation based on the pressure sensor 245 by the APC valve 244, and the temperature sensor 243, 243c, 243d, 243e, 243f, 243g, 243h, 243j, The power supply of the high frequency power supply 273, the impedance adjustment operation by the matching device 272, the operation of the rotation mechanism 267, And the operation of adjusting the rotation speed of the boat 217 by the boat elevator 115 and the elevating operation of the boat 217 by the boat elevator 115. [

The controller 121 is not limited to being a dedicated computer, and may be configured as a general-purpose computer. A magnetic tape such as a magnetic disk such as a flexible disk or a hard disk, an optical disk such as a CD or a DVD, a magneto-optical disk such as an MO, or the like, A semiconductor memory such as a USB memory or a memory card) and installing the program in a general-purpose computer by using the external storage device 123 can constitute the controller 121 according to the present embodiment . In addition, the means for supplying the program to the computer is not limited to the case of supplying via the external storage device 123. [ The program may be supplied without interposing the external storage device 123 using a communication means such as the Internet or a private line. Further, the storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, they are collectively referred to simply as a recording medium. In the present specification, the term " recording medium " includes the case where only the storage device 121c is included alone, the case where only the external storage device 123 is included alone, or both cases.

Next, a sequence example in which a thin film is formed on a substrate as one step of a manufacturing process of a semiconductor device (device) using the processing furnace of the above-described substrate processing apparatus will be described. In the following description, the operations of the respective parts constituting the substrate processing apparatus are controlled by the controller 121. [

In the embodiment of the present invention, for the purpose of making the composition ratio of the film to be formed to be a predetermined composition ratio which is different from the stoichiometric composition or the stoichiometric composition, it is preferable that a plurality of kinds of gases including a plurality of elements constituting the thin film to be formed Control the supply conditions. For example, the supply conditions are controlled for the purpose of making at least one element among the plurality of elements constituting the film to be formed to be excessive relative to the stoichiometric composition. Hereinafter, three example sequences (first sequence to third sequence) for performing film formation while controlling the ratio of a plurality of elements constituting the thin film, that is, the composition ratio of the thin film will be described.

In the first sequence of the present embodiment,

A step of supplying a first source gas containing a predetermined element and a halogen group to a substrate in the treatment chamber and a step of supplying a second source gas containing a predetermined element and an amino group to the substrate in the treatment chamber are alternately performed a predetermined number of times , A step of forming a first layer containing a predetermined element, nitrogen and carbon on the substrate; And

A step of modifying the first layer to form a second layer by supplying an amine-based source gas to the substrate in the treatment chamber;

Are alternately performed a predetermined number of times to form a thin film having a predetermined composition including a predetermined element on the substrate.

In the second sequence and the third sequence of the present embodiment,

A step of supplying a first source gas containing a predetermined element and a halogen group to a substrate in the treatment chamber and a step of supplying a second source gas containing a predetermined element and an amino group to the substrate in the treatment chamber are alternately performed a predetermined number of times , A step of forming a first layer containing a predetermined element, nitrogen and carbon on the substrate;

A step of modifying the first layer to form a second layer by supplying an amine-based source gas to the substrate in the treatment chamber; And

A step of forming a third layer by modifying the second layer by supplying a reaction gas different from each of the source gases to the substrate in the treatment chamber;

To form a thin film having a predetermined composition including a predetermined element on the substrate.

(First sequence)

First, the first sequence of the present embodiment will be described. 4 is a diagram showing an example of a film formation flow in the first sequence of the present embodiment. 7 is a diagram showing an example of timing of gas supply in the first sequence of the present embodiment.

In the first sequence of the present embodiment,

Forming a first layer containing silicon, nitrogen and carbon on the wafer 200 by alternately supplying the chlorosilane-based raw material and the aminosilane-based raw material to the wafer 200 in the treatment chamber 201; And

A step of modifying the first layer by supplying an amine-based raw material to the wafer 200 in the treatment chamber 201 to form a silicon carbonitride layer as a second layer;

Thereby forming a silicon carbide nitride film having a predetermined composition and a predetermined film thickness on the wafer 200.

Here, " alternately supplying the chlorosilane-based raw material and the aminosilane-based raw material " means that one of the raw materials of the chlorosilane-based raw material and the aminosilane-based raw material is supplied and then the other raw material is supplied, In this case, the set includes both the case of performing the set once and the case of repeating the set a plurality of times. That is, to perform this set one or more times (a predetermined number of times).

Further, "alternately performing the step of forming the first layer and the step of forming the second layer" means that, when the step of forming the first layer and the step of forming the second layer are performed in one cycle, And the case where the cycle is repeated a plurality of times. That is, this cycle is performed at least once (a predetermined number of times).

Fig. 4 and Fig. 7 show that the set consisting of the above-described set, that is, the step of supplying one of the raw materials among the chlorosilane-based raw material and the aminosilane-based raw material, and the subsequent step of supplying the other raw material, There is shown an example of a sequence in which the above-described cycle, that is, the step of forming the first layer and the step of forming the second layer are performed a predetermined number of times.

That is, in the film formation sequence of FIGS. 4 and 7, the chlorosilane-based raw material is supplied to the wafer 200 in the processing chamber 201, and then the aminosilane-based raw material is supplied, Forming a first layer comprising nitrogen and carbon; And

A step of modifying the first layer by supplying an amine-based raw material to the wafer 200 in the treatment chamber 201 to form a silicon carbonitride layer as a second layer;

Is performed alternately a predetermined number of times to form a silicon carbide nitride film having a predetermined composition and a predetermined film thickness on the wafer 200.

Hereinafter, the first sequence of the present embodiment will be described in detail. Here, HCDS gas as an aminosilane-based source gas as a chlorosilane-based source gas, 3DMAS gas as an amine-based source gas, TEA gas as a source gas, and a silicon carbide film (SiCN Film) is formed on the substrate.

In the present specification, the word " wafer " is used to mean " the wafer itself " or the case where the term " laminate (aggregate) of a predetermined layer or film formed on the wafer and its surface " A predetermined layer or a film formed on the surface is referred to as a wafer). When the word " surface of wafer " is used in this specification, " surface (exposed surface) " of the wafer itself or " surface of a predetermined layer or film formed on the wafer, Quot ;, the " outermost surface of the wafer "

Therefore, in the case of describing " supplying a predetermined gas to a wafer " in the present specification, it means that "a predetermined gas is directly supplied to the surface (exposed surface) of the wafer itself" A predetermined gas is supplied to the layer or film formed on the wafer, that is, the outermost surface of the wafer as the layered product ". In the case of "forming a predetermined layer (or film) on a wafer" in the present specification, "a predetermined layer (or film) is directly formed on the surface (exposed surface) of the wafer itself" (Or film) is formed on the top surface of the wafer as a layer or a film to be formed on the wafer, that is, a layered body, in some cases.

In this specification, the word " substrate " is used in the same way as the case of using the word " wafer ". In this case, the word " wafer "

(Wafer charge and boat load)

When a plurality of wafers 200 are loaded (wafer charged) on the boat 217, a boat 217 supporting a plurality of wafers 200 as shown in Fig. 1 is brought in by the boat elevator 115 (Boat-loaded) into the processing chamber 201. In this state, the seal cap 219 is in a state of sealing the lower end of the reaction tube 203 via the O-ring 220.

(Pressure adjustment and temperature adjustment)

And is evacuated by the vacuum pump 246 so that the pressure in the processing chamber 201 becomes a desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information (pressure adjustment). Further, the vacuum pump 246 maintains a state in which the vacuum pump 246 always operates at least until the processing for the wafer 200 is completed. And is heated by the heater 207 so that the temperature in the processing chamber 201 becomes a desired temperature. At this time, based on the temperature information detected by the temperature sensor 263 so that the temperature distribution in the processing chamber 201 becomes a desired temperature, the energization state of the heater 207 is feedback controlled (temperature adjustment). The heating in the processing chamber 201 by the heater 207 is continuously performed at least until the processing for the wafer 200 is completed. Subsequently, the boat 217 is rotated by the rotating mechanism 267 to rotate the wafer 200 (wafer rotation). The rotation of the boat 217 and the wafer 200 by the rotating mechanism 267 is continuously performed at least until the processing on the wafer 200 is completed.

(Silicon Carbonitride Film Forming Step)

Then, the next three steps, that is, steps 1 to 3, are sequentially executed.

[Step 1] (supply of HCDS gas)

The valve 243a of the first gas supply pipe 232a is opened and HCDS gas is flowed into the first gas supply pipe 232a. The HCDS gas flowing in the first gas supply pipe 232a is regulated in flow rate by the mass flow controller 241a. The HCDS gas whose flow rate is adjusted is supplied into the process chamber 201 from the gas supply hole 250a of the first nozzle 249a and is exhausted from the exhaust pipe 231. [ At this time, HCDS gas is supplied to the wafer 200. Simultaneously, the valve 243e is opened and an inert gas such as N ₂ gas is flowed into the inert gas supply pipe 232e. The flow rate of the N ₂ gas flowing in the inert gas supply pipe 232e is adjusted by the mass flow controller 241e. The flow-regulated N ₂ gas is supplied into the processing chamber 201 together with the HCDS gas, and is exhausted from the exhaust pipe 231.

At this time, valves 243f, 243g, and 243h are opened to prevent intrusion of HCDS gas into the second nozzle 249b, the third nozzle 249c, the fourth nozzle 249d, and the buffer chamber 237, N ₂ gas is passed through the second inert gas supply pipe 232f, the third inert gas supply pipe 232g, and the fourth inert gas supply pipe 232h. The N ₂ gas is supplied to the second gas supply pipe 232b, the third gas supply pipe 232c, the fourth gas supply pipe 232d, the second nozzle 249b, the third nozzle 249c, the fourth nozzle 249d, Is supplied into the processing chamber 201 through the chamber 237 and exhausted from the exhaust pipe 231. [

At this time, the APC valve 244 is suitably adjusted to set the pressure in the treatment chamber 201 to a pressure within a range of, for example, 1 Pa to 13,300 Pa, preferably 20 Pa to 1,330 Pa. The supply flow rate of the HCDS gas controlled by the mass flow controller 241a is set to a flow rate within a range of, for example, 1 sccm to 1,000 sccm. The supply flow rates of the N ₂ gas controlled by the mass flow controllers 241e, 241f, 241g, and 241h are set to flow rates within a range of, for example, 100 sccm to 10,000 sccm, respectively. The time for supplying the HCDS gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, from 1 second to 120 seconds, preferably from 1 second to 60 seconds. At this time, the temperature of the heater 207 is set to a temperature at which the temperature of the wafer 200 can be within a range of, for example, 250 to 700 占 폚, preferably 300 to 650 占 폚, and more preferably 350 to 600 占 폚 . If the temperature of the wafer 200 is less than 250 ° C, HCDS is difficult to chemically adsorb onto the wafer 200, and a practical film-forming rate may not be obtained. By making the temperature of the wafer 200 at 250 DEG C or higher, it can be solved. Further, by setting the temperature of the wafer 200 to 300 DEG C or more and 350 DEG C or more, it becomes possible to more sufficiently adsorb HCDS on the wafer 200, and a more sufficient deposition rate can be obtained. Also, when the temperature of the wafer 200 exceeds 700 ° C, the CVD reaction becomes stronger (the gas phase reaction becomes dominant), so that the uniformity of the film thickness tends to deteriorate, and control becomes difficult. By controlling the temperature of the wafer 200 to 700 占 폚 or less, the deterioration of film thickness uniformity can be suppressed and control thereof becomes possible. Particularly, by setting the temperature of the wafer 200 to 650 DEG C or lower and 600 DEG C or lower, the surface reaction becomes dominant and the uniformity of the film thickness becomes easy to be easily controlled. Therefore, the temperature of the wafer 200 is preferably set to a temperature within the range of 250 to 700 占 폚, preferably 300 to 650 占 폚, and more preferably 350 to 600 占 폚.

By supplying HCDS gas into the processing chamber 201 under the above-described conditions, a silicon-containing layer having a thickness of, for example, less than one atomic layer to several atomic layers is formed on the wafer 200 (underlying film) . The silicon-containing layer may be an adsorption layer of HCDS gas, a silicon layer (Si layer), or both. However, the silicon-containing layer is preferably a layer containing silicon (Si) and chlorine (Cl).

Here, the silicon layer is a general term including a discontinuous layer in addition to a continuous layer constituted by silicon (Si), or a silicon thin film formed by superimposing these layers. A continuous layer constituted by Si may also be referred to as a silicon thin film. The Si constituting the silicon layer also includes those in which bonding with Cl is not completely terminated.

In addition, the adsorption layer of the HCDS gas also includes a discontinuous chemical adsorption layer in addition to the chemical adsorption layer in which the gas molecules of the HCDS gas are continuous. That is, the adsorption layer of the HCDS gas includes a single molecule layer composed of HCDS molecules or a chemisorbed layer having a thickness less than one molecular layer. In addition, the HCDS (Si ₂ Cl ₆ ) molecule constituting the adsorption layer of the HCDS gas also includes a part of the bond between Si and Cl (Si _x Cl _y molecule). That is, the adsorption layer of HCDS contains a chemisorption layer or a discontinuous chemisorption layer in which Si ₂ Cl ₆ molecules and / or Si _x Cl _y molecules are continuous. Further, a layer having a thickness less than one atomic layer means an atomic layer formed discontinuously, and a layer having a thickness of one atomic layer means an atomic layer formed continuously. Further, a layer having a thickness of less than one molecular layer means a molecular layer formed discontinuously, and a layer having a thickness of one molecular layer means a molecular layer formed continuously.

Under the condition that the HCDS gas undergoes self-decomposition (pyrolysis), that is, under the condition that the thermal decomposition reaction of HCDS occurs, the silicon layer is formed by depositing Si on the wafer 200. Under the condition that the HCDS gas does not decompose (pyrolyze), that is, under the condition that the thermal decomposition reaction of the HCDS does not occur, the HCDS gas adsorbs on the wafer 200 to form the adsorption layer of the HCDS gas. Further, it is preferable to form a silicon layer on the wafer 200 rather than to form an adsorption layer of HCDS gas on the wafer 200 because the film formation rate can be made higher.

When the thickness of the silicon-containing layer formed on the wafer 200 exceeds the number of atomic layers, the effect of modification in step 3 described later is not transmitted to the entire silicon-containing layer. The minimum value of the thickness of the silicon-containing layer that can be formed on the wafer 200 is less than one atomic layer. Therefore, it is preferable that the thickness of the silicon-containing layer is less than one atomic layer to several atomic layers. Further, by making the thickness of the silicon-containing layer 1 atomic layer or less, that is, less than 1 atomic layer or 1 atomic layer, the effect of the reforming reaction in Step 3 described later can be relatively increased, and the time required for the reforming reaction in Step 3 Can be shortened. The time required for forming the silicon-containing layer in Step 1 can be shortened. As a result, the processing time per cycle can be shortened, and the total processing time can be shortened. That is, the film forming rate can be increased. Further, by controlling the thickness of the silicon-containing layer to 1 atomic layer or less, controllability of film thickness uniformity can be improved.

(Removal of residual gas)

After the silicon-containing layer is formed on the wafer 200, the valve 243a of the first gas supply pipe 232a is closed and the supply of the HCDS gas is stopped. At this time, the APC valve 244 of the exhaust pipe 231 is opened, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246 to remove the unreacted portion remaining in the processing chamber 201 or the HCDS The gas is excluded from the inside of the processing chamber 201. Further, the valves 243e, 243f, 243g, and 243h are kept in the open state to maintain the supply of the N ₂ gas as the inert gas into the processing chamber 201. The N ₂ gas acts as a purge gas, thereby further enhancing the effect of eliminating HCDS gas remaining in the processing chamber 201 or contributing to formation of the silicon-containing layer from within the processing chamber 201.

At this time, the gas remaining in the processing chamber 201 may not be entirely excluded, or the processing chamber 201 may not be completely purged. If there is a small amount of gas remaining in the processing chamber 201, there is no adverse effect in step 2 performed after that. At this time, the flow rate of the N ₂ gas to be supplied into the process chamber 201 is not limited to a large flow rate. For example, by supplying an amount of the same amount as the volume of the reaction tube 203 (process chamber 201) It is possible to carry out purging to such an extent that adverse effects do not occur. By not completely purging the inside of the processing chamber 201, the purging time can be shortened and the throughput can be improved. In addition, it becomes possible to suppress the consumption of N ₂ gas to the minimum necessary.

As the chlorosilane-based source gas, tetrachlorosilane (SiCl ₄ , abbreviation: STC) gas, trichlorosilane (SiHCl ₃ , abbreviation: TCS) gas, dichlorosilane (SiH ₂ Cl ₂ , abbreviation: DCS) gas, and monochlorosilane (SiH ₃ Cl, abbreviation: MCS) gas may be used. As the inert gas, a rare gas such as Ar gas, He gas, Ne gas or Xe gas may be used in addition to N ₂ gas.

[Step 2] (supply of 3DMAS gas)

After the step 1 is completed and the residual gas in the processing chamber 201 is removed, the valve 243b of the second gas supply pipe 232b is opened and the 3DMAS gas is flowed into the second gas supply pipe 232b. The 3DMAS gas flowing in the second gas supply pipe 232b is regulated in flow rate by the mass flow controller 241b. The 3DMAS gas whose flow rate has been adjusted is supplied from the gas supply hole 250b of the second nozzle 249b into the process chamber 201 and exhausted from the exhaust pipe 231. [ At this time, 3DMAS gas is supplied to the wafer 200. At this time, the valve 243f is opened and N ₂ gas is passed through the inert gas supply pipe 232f. The N ₂ gas is supplied into the processing chamber 201 together with the 3DMAS gas and exhausted from the exhaust pipe 231.

At this time, the valves 243e, 243g, and 243h are opened to prevent the inflow of the 3DMAS gas into the first nozzle 249a, the third nozzle 249c, the fourth nozzle 249d, and the buffer chamber 237, N ₂ gas is passed through the first inert gas supply pipe 232e, the third inert gas supply pipe 232g, and the fourth inert gas supply pipe 232h. The N ₂ gas is supplied to the first gas supply pipe 232a, the third gas supply pipe 232c, the fourth gas supply pipe 232d, the first nozzle 249a, the third nozzle 249c, the fourth nozzle 249d, Is supplied into the processing chamber 201 through the chamber 237 and exhausted from the exhaust pipe 231. [

At this time, the APC valve 244 is appropriately adjusted so that the pressure in the treatment chamber 201 is set to a pressure within a range of, for example, 1 Pa to 13,300 Pa, preferably 20 Pa to 1,330 Pa, The supply flow rate of the 3DMAS gas controlled by the mass flow controller 241b is set to a flow rate within a range of, for example, 1 sccm to 1,000 sccm. The supply flow rates of the N ₂ gas controlled by the mass flow controllers 241f, 241e, 241g, and 241h are set to flow rates within a range of, for example, 100 sccm to 10,000 sccm, respectively. The time for supplying the 3DMAS gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, a time within the range of 1 second to 120 seconds, preferably 1 second to 60 seconds. The temperature of the heater 207 at this time is set to a temperature within the range of 250 to 700 占 폚, preferably 300 to 650 占 폚, and more preferably 350 to 600 占 폚, Lt; / RTI >

By the supply of the 3DMAS gas, the silicon-containing layer formed on the wafer 200 in Step 1 reacts with the 3DMAS gas. Whereby the silicon-containing layer is reformed into a first layer comprising silicon (Si), nitrogen (N) and carbon (C). The first layer is a layer containing Si, N and C with thicknesses of less than one atomic layer to several atomic layers. Further, the first layer is a layer having a relatively large proportion of the Si component and the C component, that is, a Si rich layer and a C rich layer.

(Removal of residual gas)

After the first layer is formed on the wafer 200, the valve 243b of the second gas supply pipe 232b is closed and the supply of the 3DMAS gas is stopped. At this time, the APC valve 244 of the exhaust pipe 231 is opened and the inside of the processing chamber 201 is evacuated by the vacuum pump 246 so as to be unreacted in the processing chamber 201, 3DMAS gas or reaction by-products are excluded from the inside of the processing chamber 201. [ In addition, the valves 243f, 243e, 243g, and 243h are kept in the open state, and supply of N ₂ gas as an inert gas into the processing chamber 201 is maintained. The N ₂ gas acts as a purge gas, thereby further enhancing the effect of eliminating the unreacted residual in the processing chamber 201 or the 3DMAS gas or the reaction by-product after the contribution to the formation of the first layer from the inside of the processing chamber 201 .

At this time, the gas remaining in the processing chamber 201 may not be entirely excluded, or the processing chamber 201 may not be completely purged. If there is a small amount of gas remaining in the processing chamber 201, there is no adverse effect in step 3 performed after that. At this time, the flow rate of the N ₂ gas to be supplied into the process chamber 201 is not limited to a large flow rate. For example, by supplying the same amount as the volume of the reaction tube 203 (processing chamber 201) It is possible to carry out purging to such an extent that adverse effects do not occur. By not completely purging the inside of the processing chamber 201, the purging time can be shortened and the throughput can be improved. In addition, it becomes possible to suppress the consumption of N ₂ gas to the minimum necessary.

As the aminosilane-based source gas, besides the 3DMAS gas, tetrakisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₄ , abbreviation: 4DMAS) gas, bisdiethylaminosilane (Si [N (C ₂ H ₅ ) ₂ ] ₂ H _2, abbreviation: 2DEAS) gas, a non-master-tertiary butyl amino silane _{(SiH 2 [NH (C 4} H 9)] 2, abbreviated: BTBAS) gas, hexamethyldisilazane _{[(CH 3) 3 Si-} NH- Si (CH ₃ ) ₃ , abbreviation: HMDS] gas may be used. As the inert gas, a rare gas such as Ar gas, He gas, Ne gas or Xe gas may be used in addition to N ₂ gas.

[Step 3] (TEA gas supply)

Step 2 is completed and the residual gas or reaction by-products in the processing chamber 201 are removed. Then, the valve 243c of the third gas supply pipe 232c is opened and TEA gas is supplied into the third gas supply pipe 232c. The flow rate of the TEA gas flowing through the third gas supply pipe 232c is adjusted by the mass flow controller 241c. The flow rate adjusted TEA gas is supplied into the process chamber 201 from the gas supply hole 250c of the third nozzle 249c and exhausted from the exhaust pipe 231. [ At this time, TEA gas is supplied to the wafer 200. At the same time, the valve 243g is opened and N ₂ gas is passed through the inert gas supply pipe 232g. The N ₂ gas is supplied into the processing chamber 201 together with the TEA gas and exhausted from the exhaust pipe 231.

At this time, the valves 243e, 243f, 243h are opened to prevent the inflow of the TEA gas into the first nozzle 249a, the second nozzle 249b, the fourth nozzle 249d and the buffer chamber 237, N ₂ gas is passed through the first inert gas supply pipe 232e, the second inert gas supply pipe 232f and the fourth inert gas supply pipe 232h. The N ₂ gas is supplied to the first gas supply pipe 232a, the second gas supply pipe 232b, the fourth gas supply pipe 232d, the first nozzle 249a, the second nozzle 249b, the fourth nozzle 249d, Is supplied into the processing chamber 201 through the chamber 237 and exhausted from the exhaust pipe 231. [

At this time, the APC valve 244 is suitably adjusted to set the pressure in the treatment chamber 201 to a pressure within a range of, for example, 1 Pa to 13,300 Pa, preferably 500 Pa to 6,000 Pa. The supply flow rate of the TEA gas to be controlled by the mass flow controller 241c is set to a flow rate within a range of, for example, 1 sccm to 10,000 sccm. The supply flow rates of the N ₂ gas controlled by the mass flow controllers 241g, 241e, 241f, and 241h are set to flow rates within a range of, for example, 100 sccm to 10,000 sccm, respectively. The time for supplying the TEA gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, from 1 second to 120 seconds, preferably from 1 second to 60 seconds. The temperature of the heater 207 at this time is set to a temperature of the wafer 200 of 250 to 700 ° C, preferably 300 to 650 ° C, more preferably 350 to 600 ° C Set the temperature to the temperature within the range. The TEA gas is activated (excited) in the third nozzle 249c or in the process chamber 201 to be supplied to the wafer 200. Further, it is possible to softly react the TEA gas by supplying the TEA gas by activating it with heat, so that the following modification process can be softly performed.

By the supply of the TEA gas, TEA gas reacts with at least a part of the first layer including Si, N and C having a relatively large proportion of Si component and C component on the wafer 200 in Step 2. Whereby the first layer is modified into a second layer. At this time, the ratio of the Si component of the first layer decreases due to the reaction between the first layer and the TEA gas, the proportion of the component C increases, and the proportion of the component N increases. Further, the impurity component such as Cl contained in the first layer is removed from the layer by this reaction.

That is, by supplying the thermally activated TEA gas to the wafer 200, the ratio of the C component and the N component in the first layer is increased, and the impurity component such as Cl in the first layer is removed The first layer can be reformed into the second layer. And the second layer becomes a silicon carbonitride layer (SiCN layer) having a thickness of less than one atomic layer to several atomic layers. The second layer becomes a C-rich layer than the first layer and becomes a layer having less impurities such as Cl than the first layer. In this way, the reforming treatment for the first layer is performed by the TEA gas.

The pressure in the process chamber 201 when the TEA gas is supplied to the wafer 200 is set to be larger than the pressure in the process chamber 201 when the HCDS gas and the 3DMAS gas are supplied to the wafer 200 in steps 1 and 2 . The pressure in the processing chamber 201 when the HCDS gas and the 3DMAS gas are supplied to the wafer 200 is P ₁ and P ₂ [Pa], respectively, and the processing chamber 201 when the TEA gas is supplied to the wafer 200 Is set to P ₃ [Pa], it is preferable that the pressure P ₁ to the pressure P ₃ are set so as to satisfy the relationship P ₃ > P ₁ and P ₂ , respectively. That is, it is preferable that the pressure in the process chamber 201 when the TEA gas is supplied to the wafer 200 is the highest in steps 1 to 3. The ratio of the C component in the SiCN layer can be made larger than the ratio of the N component by setting the pressure in the processing chamber 201 at the time of supplying the TEA gas to such a pressure and it is possible to form a C rich SiCN layer It becomes possible.

(Removal of residual gas)

Thereafter, the valve 243c of the third gas supply pipe 232c is closed, and the supply of the TEA gas is stopped. At this time, the APC valve 244 of the exhaust pipe 231 is opened, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246 so as to be unreacted remaining in the processing chamber 201, TEA gas or reaction by-products are excluded from the inside of the processing chamber 201. In addition, the valves 243g, 243e, 243f, and 243h are kept in the open state to maintain the supply of N ₂ gas as the inert gas into the processing chamber 201. The N ₂ gas acts as a purge gas, thereby further enhancing the effect of eliminating the unreacted residual in the processing chamber 201 or the TEA gas or the reaction by-product after the contribution to the formation of the second layer from the inside of the processing chamber 201 .

At this time, the gas remaining in the processing chamber 201 may not be entirely excluded, or the processing chamber 201 may not be completely purged. If there is a small amount of gas remaining in the processing chamber 201, no adverse effect occurs in step 1 performed thereafter. At this time, the flow rate of the N ₂ gas to be supplied into the processing chamber 201 is not limited to a large flow rate. For example, by supplying the same amount as the volume of the reaction tube 203 (processing chamber 201) It is possible to carry out purging to such an extent that adverse effects do not occur. By not completely purging the inside of the processing chamber 201, the purging time can be shortened and the throughput can be improved. In addition, it becomes possible to suppress the consumption of N ₂ gas to the minimum necessary.

Amine-based raw material gas as triethylamine _{[(C 2 H 5) 3} N, abbreviation: TEA] In addition to di-ethylamine _{[(C 2 H 5) 2} NH, abbreviated: DEA], monoethylamine (C ₂ H ₅ NH _2, abbreviation: MEA) such as amine-based source gas, trimethylamine [(CH _{3) 3} N, abbreviation: TMA] vaporizing, dimethylamino [(CH _{3) 2} NH, abbreviated: DMA], mono-methyl-amine ( CH ₃ NH _2, abbreviation: MMA) of methyl amine-based material gas, tripropyl vaporizing the amine _{[(C 3 H 7) 3} N, abbreviation: TPA], dipropyl amine _{[(C 3 H 7) 2} NH, Propylamine ([(CH ₃ ) ₂ CH] ₃ N, abbreviation: TIPA), which is obtained by vaporizing a propylamine-based source gas in which propyleneamine (abbreviation: DPA) and monopropylamine (C ₃ H ₇ NH ₂ , abbreviated as MPA) , An isopropylamine-based feed gas in which diisopropylamine ([(CH ₃ ) ₂ CH ₂ NH, abbreviation: DIPA) and monoisopropylamine [(CH ₃ ) ₂ CHNH ₂ , abbreviated as MIPA] (C ₄ H ₉ ) ₂ N, abbreviated as TBA], dibutylamine [(C ₄ H ₉ ) ₂ NH, abbreviated as DBA], monobutylamine (C ₄ H ₉ NH ₂ , abbreviated as MBA ) ([(CH ₃ ) ₂ CHCH ₂ ] ₃ NH, abbreviation: TIBA), diisobutylamine ([(CH ₃ ) ₂ CHCH ₂ ] ₂ NH, Isobutylamine-based source gas in which monoisobutylamine [(CH ₃ ) ₂ CHCH ₂ NH ₂ , abbreviation: MIBA] and the like are vaporized can be preferably used. I.e. Examples of amine-based material gas _{(C 2 H 5) x NH} 3-x, (CH 3) x NH 3-x, (C 3 H 7) x NH 3-x, [(CH 3) 2 CH] x At least one gas of NH _{3 -x} , (C ₄ H ₉ ) _x NH _{3 -x} , [(CH ₃ ) ₂ CHCH ₂ ] _x NH _{3 -x} (wherein x is an integer of 1 to 3) Can be used to make. As the inert gas, a rare gas such as Ar gas, He gas, Ne gas or Xe gas may be used in addition to N ₂ gas.

Instead of the amine-based source gas, a gas containing an organic hydrazine compound, that is, an organic hydrazine-based gas, may be used as a raw material gas containing carbon and nitrogen. The organic hydrazine gas is a gas containing a hydrazine group such as a gas obtained by vaporizing an organic hydrazine, and is a gas containing carbon (C), nitrogen (N), and hydrogen (H). That is, the organic hydrazine-based gas is a silicon-free gas and also contains no silicon and no metal. Examples of the organic hydrazine-based gas, for example monomethyl hydrazine _{[(CH 3) HN 2 H} 2, abbreviation: MMH], dimethyl hydrazine _{[(CH 3) 2 N 2} H 2, abbreviation: DMH], trimethyl hydrazine [(CH _{3) 2} N ₂ (CH ₃₎ H, abbreviation: TMH] a methyl hydrazine gas or ethyl hydrazine vaporization and the like _{[(C 2 H 5) HN} 2 H 2, abbreviated as: EH] such as preferably an ethyl hydrazine-based gas vaporizing Can be used to make. Further, in the case of using organic hydrazine in a liquid state at room temperature and atmospheric pressure, such as MMH, the organic hydrazine in a liquid state is vaporized by a vaporization system such as a vaporizer or a bubbler to generate an organic hydrazine gas, MMH gas). Further, a gas containing an organic hydrazine compound may be simply referred to as an organic hydrazine compound gas or an organic hydrazine gas.

(A predetermined number of times)

A silicon nitride film (SiCN film) of a predetermined composition and a predetermined film thickness can be formed on the wafer 200 by performing the above-described steps 1 to 3 in one cycle and performing this cycle one or more times (a predetermined number of times) . It is also preferable that the above cycle is repeated a plurality of times. That is, the SiCN layer formed per cycle is made smaller than the desired film thickness, and the cycle is repeated a plurality of times until a desired film thickness is obtained. The SiCN film may also be referred to as a thin film containing silicon (Si), carbon (C) and nitrogen (N).

In the case where the cycle is performed a plurality of times, the portion described as "supplying a predetermined gas to the wafer 200" in each of the steps after the second cycle is " A predetermined gas is supplied to the outermost surface of the wafer 200 as a layered product ", and a portion described as" forming a predetermined layer on the wafer 200 " That is, a predetermined layer is formed on the outermost surface of the wafer 200 as a layered body. &Quot; This point is as described above. This point is also true for each modification example, each application example, another film formation sequence, and other embodiments described later.

The step of alternately performing Step 1 and Step 2 described above a predetermined number of times and the step of performing Step 3 are alternately performed a predetermined number of times to form SiCN having a predetermined composition and a predetermined film thickness on the wafer 200 A film may be formed. That is, by performing the above-described steps 1 and 2 as one set and performing this set a predetermined number of times and performing the step 3 as one cycle and performing this cycle a predetermined number of times, A SiCN film having a film thickness may be formed.

The control of the composition ratio of the SiCN film can be improved by performing this cycle a predetermined number of times with one cycle of the step of performing the set number of times and the step of performing the step 3 with the steps 1 and 2 described above as one set, . The absolute amount of the silicon component, the nitrogen component and the carbon component of the first layer can be increased or decreased by increasing or decreasing the number of sets constituted in steps 1 and 2. In this way, By modifying in step 3, the ratio of each component of the SiCN layer can be adjusted by the number of sets, and the ratio of each component of the finally formed SiCN film can be controlled by the number of sets.

Further, by increasing the number of sets constituted in steps 1 and 2, it is possible to increase the number of layers of the first layer formed per cycle, that is, the thickness of the first layer formed per cycle, by the number of sets, (The thickness of the SiCN layer formed per unit cycle) can be improved. In this way, the film-forming rate (film thickness of the SiCN film formed per unit time) can be improved.

(Purge and atmospheric pressure return)

An inert gas such as N ₂ is supplied into the processing chamber 201 and exhausted from the exhaust pipe 231 so that the processing chamber 201 is filled with an inert gas The gas or reaction by-products remaining in the process chamber 201 are removed from the process chamber 201 (gas purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure return).

(Boat unload and wafer discharge)

Thereafter, the seal cap 219 is lowered by the boat elevator 115 to open the lower end of the reaction tube 203, and the processed wafer 200 is supported by the boat 217 in the reaction tube (Boat unloading) from the lower end of the reaction tube 203 to the outside of the reaction tube 203. Thereafter, the processed wafer 200 is taken out from the boat 217 (wafer discharge).

(Second sequence)

Next, the second sequence of the present embodiment will be described. 5 is a diagram showing an example of the film formation flow in the second sequence of the present embodiment. 8 is a diagram showing an example of timing of gas supply in the second sequence of the present embodiment.

In the second sequence of the present embodiment,

Forming a first layer containing silicon, nitrogen and carbon on the wafer 200 by alternately supplying the chlorosilane-based raw material and the aminosilane-based raw material to the wafer 200 in the treatment chamber 201;

A step of modifying the first layer by supplying an amine-based raw material to the wafer 200 in the treatment chamber 201 to form a silicon carbonitride layer as a second layer; And

Oxidizing the second layer by supplying heat-activated oxygen-containing gas (oxidizing gas) to the wafer 200 in the processing chamber 201 to form a silicon oxynitride layer or a silicon oxynitride layer as a third layer;

To form a silicon oxynitride film or a silicon oxynitride film having a predetermined composition and a predetermined film thickness on the wafer 200. [

Here, " alternately supplying the chlorosilane-based raw material and the aminosilane-based raw material " means that one of the raw materials of the chlorosilane-based raw material and the aminosilane-based raw material is supplied and then the other raw material is supplied, In this case, the set includes both the case of performing the set once and the case of repeating the set a plurality of times. That is, to perform this set one or more times (a predetermined number of times).

Further, the phrase " a cycle including the step of forming the first layer, the step of forming the second layer and the step of forming the third layer " is performed a predetermined number of times " When the step of forming the third layer and the step of forming the third layer are taken as one cycle, this includes both the case of performing this cycle once and the case of repeating this cycle a plurality of times. That is, this cycle is performed at least once (a predetermined number of times).

Figs. 5 and 8 are a set of one set consisting of the above-described set, that is, the step of supplying one raw material out of the chlorosilane-based raw material and the aminosilane-based raw material, and thereafter the step of supplying the other raw material, There is shown an example of a sequence in which the above-described cycle, that is, the process of forming the first layer, the process of forming the second layer, and the process of forming the third layer is performed a predetermined number of times.

That is, in the film formation sequence of Figs. 5 and 8,

A first layer containing silicon, nitrogen, and carbon is formed on the wafer 200 by supplying the chlorosilane-based raw material to the wafer 200 in the treatment chamber 201 and then supplying the aminosilane-based raw material to the wafer 200 in the treatment chamber 201 ;

A step of modifying the first layer by supplying an amine-based source gas to the wafer (200) in the treatment chamber (201) to form a silicon carbonitride layer as a second layer; And

Oxidizing the second layer by supplying heat-activated oxygen-containing gas to the wafer (200) in the processing chamber (201) to form a silicon oxynitride layer or a silicon oxynitride layer as a third layer;

To form a silicon oxynitride film or a silicon oxynitride film having a predetermined composition and a predetermined film thickness on the wafer 200. [

Hereinafter, the second sequence of the present embodiment will be described in detail. Here, HCDS gas is used as the chlorosilane-based source gas, 3DMAS gas is used as the aminosilane-based source gas, TEA gas is used as the amine-based source gas, and O ₂ gas is used as the oxygen-containing gas. A silicon oxynitride film (SiOCN film) or a silicon oxynitride layer (SiOC film) is formed as an insulating film on a substrate.

Wafer charge, boat load, pressure adjustment, temperature adjustment, and wafer rotation are performed in the same manner as the first sequence. Thereafter, the following four steps are sequentially executed.

[Step 1]

Step 1 is performed in the same manner as Step 1 of the first sequence. That is, the processing conditions in step 1, the reaction to be generated, the layer to be formed, and the like are the same as those in step 1 in the first sequence. That is, in this step, the silicon-containing layer is formed on the wafer 200 by supplying the HCDS gas into the process chamber 201.

[Step 2]

Step 2 is performed in the same manner as step 2 of the first sequence. That is, the processing conditions in step 2, the reaction to be generated, the layer to be formed, and the like are the same as those in step 2 in the first sequence. That is, in this step, the silicon-containing layer and the 3DMAS gas are reacted by supplying the 3DMAS gas into the processing chamber 201 to form the first layer containing Si, N and C.

[Step 3]

Step 3 is performed in the same manner as step 3 of the first sequence. That is, the processing conditions in step 3, the reaction to be generated, the layer to be formed, and the like are the same as those in step 3 in the first sequence. That is, in this step, the first layer containing Si, N and C is reacted with the TEA gas by the supply of the TEA gas into the treatment chamber 201, so that the ratio of the C component is larger than that of the first layer, (SiCN layer) having a smaller impurity component than the first layer.

The pressure in the process chamber 201 when the TEA gas is supplied to the wafer 200 is set to be larger than the pressure in the process chamber 201 when the HCDS gas and the 3DMAS gas are supplied to the wafer 200 in steps 1 and 2 And it is preferable that the pressure in the processing chamber 201 at the time of supplying O ₂ gas to the wafer 200 is larger than that in the step 4 described later. The pressure in the processing chamber 201 when O ₂ gas is supplied to the wafer 200 in Step 4 is set to be higher than the pressure in the processing chamber 201 when supplying HCDS gas and 3DMAS gas to the wafer 200 in Step 1 and Step 2. [ The pressure in the processing chamber 201 when the TEA gas is supplied to the wafer 200 is lower than the pressure in the processing chamber 201 when the O ₂ gas is supplied to the wafer 200 in step 4 . The pressure in the processing chamber 201 when the HCDS gas and the 3DMAS gas are supplied to the wafer 200 is P ₁ and P ₂ [Pa], respectively, and the TEA gas is supplied to the processing chamber 201 ) for the pressure in the P ₃ [Pa] as, and when the pressure in the process chamber 201 when the supply for the O ₂ gas to the wafer 200 to the P ₄ [Pa], the pressure P ₁ to a pressure P ₄ P _3> preferably each set so as to satisfy the relation of P _1, P _2, and further more preferable that each set so as to satisfy the relationship of P _3> P _4, and also P _3> P _4> P _1, P < ₂ &_gt; are satisfied. That is, it is preferable that the pressure in the process chamber 201 when the TEA gas is supplied to the wafer 200 is the highest in steps 1 to 4.

The ratio of the C component in the second layer (SiCN layer) can be made larger than the ratio of the N component by setting the pressure in the processing chamber 201 at the time of supplying the TEA gas to such a pressure, and the C rich SiCN It becomes possible to form a layer. Thus, even after the second layer (the SiCN layer) is oxidized in Step 4, it is possible to maintain the state where the ratio of the C component is larger than the ratio of the N component, and it is possible to form the SiOCN layer or the SiOC layer with a high C concentration . That is, a SiOCN film or SiOC film having a high C concentration can be formed. Further, in step 4, it is possible to form a state in which the ratio of the C component is larger than that of the O component after the oxidation of the second layer (SiCN layer), and a SiOCN layer or SiOC layer higher in C concentration than the O concentration It becomes possible. That is, a SiOCN film or a SiOC film having a higher C concentration than the O concentration can be formed.

[Step 4] (supply of O ₂ gas)

Step 3 is completed and the residual gas in the processing chamber 201 is removed and then the valve 243j of the fifth gas supply pipe 232j is opened and O ₂ gas is flowed into the fifth gas supply pipe 232j. The O ₂ gas flowing in the fifth gas supply pipe 232j is regulated in flow rate by the mass flow controller 241j. The adjusted O ₂ gas is supplied from the gas supply hole 250d of the fourth nozzle 249d to the processing chamber 201 through the buffer chamber 237 and exhausted from the exhaust pipe 231. [ At this time, O ₂ gas is supplied to the wafer 200. Simultaneously, the valve 243h is opened and N ₂ gas is flowed into the inert gas supply pipe 232h. The N ₂ gas is supplied into the processing chamber 201 together with the O ₂ gas and exhausted from the exhaust pipe 231.

At this time, valves 243e, 243f and 243g are opened to prevent the inflow of O ₂ gas into the first nozzle 249a, the second nozzle 249b and the third nozzle 249c, and the first inert gas supply pipe N ₂ gas is passed through the second inert gas supply pipe 232f, the second inert gas supply pipe 232f and the third inert gas supply pipe 232g. The N ₂ gas is supplied through the first gas supply pipe 232a, the second gas supply pipe 232b, the third gas supply pipe 232c, the first nozzle 249a, the second nozzle 249b and the third nozzle 249c And is then exhausted from the exhaust pipe 231. [

At this time, the APC valve 244 is appropriately adjusted to set the pressure in the processing chamber 201 to a pressure within a range of, for example, 1 Pa to 3,000 Pa. The O ₂ gas can be thermally activated in the fourth nozzle 249d or in the buffer chamber 237 or in the process chamber 201 by non-plasma by setting the pressure in the process chamber 201 to a comparatively high pressure ). In addition, the O ₂ gas can be softly reacted by supplying the O ₂ gas in the form of heat, so that oxidation to be described later can be performed softly. The supply flow rate of the O ₂ gas controlled by the mass flow controller 241j is set to a flow rate within a range of, for example, 100 sccm to 10,000 sccm. The supply flow rates of the N ₂ gas to be controlled by the mass flow controllers 241h, 241e, 241f, and 241g are each set to a flow rate within a range of, for example, 100 sccm to 10,000 sccm. At this time, the partial pressure of the O ₂ gas in the treatment chamber 201 is set to a pressure within the range of 0.01 Pa to 2,970 Pa. The time for supplying the O ₂ gas activated by the heat to the wafer 200, that is, the gas supply time (irradiation time) is, for example, a time within a range of 1 second to 120 seconds, preferably 1 second to 60 seconds. The temperature of the heater 207 at this time is set such that the temperature of the wafer 200 is, for example, 250 DEG C to 700 DEG C, preferably 300 DEG C to 650 DEG C, more preferably 350 DEG C to 600 DEG C Set the temperature to the temperature within the range.

At this time, the gas flowing into the processing chamber 201 is an O ₂ gas thermally activated by increasing the pressure in the processing chamber 201, and neither HCDS gas nor 3DMAS gas nor TEA gas is spilled into the processing chamber 201. Therefore, the O ₂ gas does not cause a gas phase reaction, and the activated O ₂ gas reacts with at least a part of the second layer (SiCN layer) formed on the wafer 200 in Step 3. Whereby the second layer is oxidized and reformed into a third layer. The third layer is a silicon oxyanitride layer (SiOCN layer) or a silicon oxynitride layer (SiOC layer).

Further, the O ₂ gas can be thermally activated and flowed into the processing chamber 201, whereby the second layer can be reformed (changed) into a SiOCN layer or SiOC layer by thermal oxidation. At this time, the second layer is modified into the SiOCN layer or the SiOC layer while adding the O component to the second layer. At this time, Si-O bonds in the second layer increase due to the action of thermal oxidation by O ₂ gas, while Si-N bonds, Si-C bonds and Si-Si bonds decrease, and in the second layer The ratio of the N component, the ratio of the C component, and the ratio of the Si component decrease. At this time, by extending the thermal oxidation time or increasing the oxidizing power of the thermal oxidation by the O ₂ gas, most of the N component can be desorbed and the N component can be reduced to the impurity level or the N component can be substantially destroyed . That is, the second layer can be modified into the SiOCN layer or the SiOC layer while varying the composition ratio in the direction of increasing the oxygen concentration and decreasing the nitrogen concentration, the carbon concentration and the silicon concentration. At this time, the ratio of the O component in the SiOCN layer or the SiOC layer, that is, the oxygen concentration can be finely adjusted by controlling the process conditions such as the pressure in the process chamber 201 and the gas supply time, Or the composition ratio of the SiOC layer can be more strictly controlled.

It was also found that the C component in the first layer formed by Step 1 and Step 2 is in a rich state as compared with the N component. In the second layer formed by Step 3, the C component becomes richer than the first layer. In some experiments, the carbon concentration was more than twice the nitrogen concentration. That is, when the C component and the N component in the second layer are desorbed by the energy of the oxidizing species (the action of thermal oxidation by the O ₂ gas), before the N component in the second layer completely desorbs, By stopping the oxidation in the remaining state, the C component and the N component remain in the second layer, and the second layer is modified into the SiOCN layer. Also, when the C component and the N component in the second layer are desorbed by the energy of the oxidizing species, the C component remains in the second layer even when most of the N component is desorbed, and by stopping the oxidation in this state The second layer is modified with a SiOC layer. That is, by controlling the gas supply time (oxidation treatment time), the ratio of the C component and the ratio of the N component, that is, the carbon concentration and the nitrogen concentration can be controlled and any one of the SiOCN layer and the SiOC layer can be controlled . Further, the ratio of the C component and the ratio of the N component, that is, the carbon concentration and the nitrogen concentration can be controlled by controlling the oxidizing power when the second layer is thermally oxidized. At this time, the ratio of the C component and the ratio of the N component in the SiOCN layer or the SiOC layer, that is, the carbon concentration and the nitrogen concentration can be finely adjusted by controlling the treatment conditions such as the pressure in the treatment chamber 201. [

At this time, it is preferable that the oxidation reaction of the second layer is not saturated. For example, in the case where the second layer of the thickness of the atomic atom layer is formed in Step 1 to Step 3, it is preferable to oxidize a part of the second layer. In this case, oxidation is performed under the condition that the oxidation reaction of the second layer becomes unsaturated so as not to oxidize the entire second layer of the thickness of the atomic atom layer.

In order to make the oxidation reaction of the second layer unsaturated, the treatment conditions in step 4 may be set to the above-described treatment conditions, and the oxidation conditions in the second layer may be unsaturated .

Wafer temperature: 500 ° C to 600 ° C

Pressure in the treatment chamber: 133 Pa to 2,666 Pa

O ₂ gas partial pressure: 33 Pa to 2,515 Pa

O ₂ gas supply flow rate: 1,000 sccm to 5,000 sccm

N ₂ gas supply flow rate: 300 sccm to 3,000 sccm

O ₂ gas supply time: 6 to 60 seconds

(Removal of residual gas)

After the third layer is formed on the wafer 200, the valve 243j of the fifth gas supply pipe 232j is closed and the supply of the O ₂ gas is stopped. At this time, the APC valve 244 of the exhaust pipe 231 is opened, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246 so as to be unreacted remaining in the processing chamber 201, O ₂ gas and reaction by-products are excluded from the inside of the processing chamber 201. Further, the valves 243h, 243e, 243f, and 243g are kept in the open state to maintain the supply of the N ₂ gas as the inert gas into the processing chamber 201. The N ₂ gas acts as a purge gas, thereby further enhancing the effect of eliminating O ₂ gas or reaction by-products remaining in the processing chamber 201 or an unreacted portion remaining in the processing chamber 201 have.

At this time, the gas remaining in the processing chamber 201 may not be entirely excluded, or the processing chamber 201 may not be completely purged. If there is a small amount of gas remaining in the processing chamber 201, no adverse effect occurs in step 1 performed thereafter. At this time, the flow rate of the N ₂ gas to be supplied into the processing chamber 201 is not limited to a large flow rate. For example, by supplying the same amount as the volume of the reaction tube 203 (processing chamber 201) It is possible to carry out purging to such an extent that adverse effects do not occur. By not completely purging the inside of the processing chamber 201, the purging time can be shortened and the throughput can be improved. In addition, it becomes possible to suppress the consumption of N ₂ gas to the minimum necessary.

The oxygen-containing gas as the nitrous oxide addition to the gas to heat activate the O ₂ gas (N ₂ O) gas, nitrogen monoxide (NO) gas and nitrogen dioxide (NO ₂₎ gas, ozone (O ₃₎ gas, hydrogen (H ₂₎ gas + It is possible to use a gas in which heat is activated by oxygen (O ₂ ) gas, H ₂ gas + O ₃ gas, water vapor (H ₂ O) gas, carbon monoxide (CO) gas, carbon dioxide (CO ₂ ) gas, A gas diluted with a rare gas such as an Ar gas, a He gas, an Ne gas, or an Xe gas may be activated by heat.

(A predetermined number of times)

By carrying out the above-described steps 1 to 4 in one cycle and performing this cycle one or more times (a predetermined number of times), a silicon oxynitride film (SiOCN film) having a predetermined composition and a predetermined film thickness, or a silicon oxyanitride film (SiOC film) can be formed. It is also preferable that the above cycle is repeated a plurality of times. That is, the thickness of the SiOCN layer or the SiOC layer formed per cycle is made smaller than the desired film thickness, and the cycle is repeated a plurality of times until a desired film thickness is obtained. The SiOCN film may also be referred to as a thin film containing silicon (Si), oxygen (O), carbon (C) and nitrogen (N). The SiOC film may also be referred to as a thin film containing silicon (Si), oxygen (O), and carbon (C).

Further, by performing the cycle including the step of alternately performing Step 1 and Step 2 described above a predetermined number of times, the step of performing Step 3, and the step of performing Step 4, A SiOCN film or a SiOC film of a predetermined composition and a predetermined film thickness may be formed. That is, the steps of performing the set number of times, performing the step 3, and performing the step 4 in one set of the steps 1 and 2 described above are performed one cycle, and the cycle is performed a predetermined number of times , A SiOCN film or a SiOC film having a predetermined film thickness may be formed on the wafer 200.

By carrying out this cycle a predetermined number of times with one cycle of performing the set number of times, performing the step 3, and performing the step 4 with one set of the steps 1 and 2 described above, The controllability of the composition ratio of the SiOCN film or the SiOC film can be improved. The absolute amount of the silicon component, the nitrogen component and the carbon component of the first layer can be increased or decreased by increasing or decreasing the number of sets constituted in steps 1 and 2. In this way, The ratio of each component of the SiOCN layer or the SiOC layer can be adjusted by the number of sets by modifying in the step 3 and the step 4 so that the ratio of each component of the finally formed SiOCN film or SiOC film can be controlled by the number of sets have.

Further, by increasing the number of sets constituted in steps 1 and 2, it is possible to increase the number of layers of the first layer formed per cycle, that is, the thickness of the first layer formed per cycle, by the number of sets, The thickness of the SiOCN layer or SiOC layer formed per cycle) can be improved. This also improves the deposition rate (the thickness of the SiOCN film or the SiOC film formed per unit time).

In addition, by performing this cycle a predetermined number of times with one cycle of the step of performing this set a predetermined number of times and the step of performing the step 4 by using the above-described steps 1 to 3 as one set, A SiOCN film or a SiOC film of a film thickness may be formed.

By performing this cycle a predetermined number of times with one cycle of the step of performing the set number of times and the step of performing step 4 with the above-described steps 1 to 3 as one set, the control of the composition ratio of the SiOCN film or the SiOC film It is possible to improve the property. The absolute amount of the silicon component, the nitrogen component and the carbon component of the second layer can be increased or decreased by increasing or decreasing the number of sets constituted by the steps 1 to 3. In this way, The ratio of each component of the SiOCN layer or the SiOC layer can be adjusted by the number of sets by modifying in step 4 and the ratio of each component of the finally formed SiOCN film or SiOC film can be controlled by the number of sets.

Further, by increasing the number of sets constituted in steps 1 to 3, it is possible to increase the number of layers of the second layer formed per cycle, that is, the thickness of the second layer formed per cycle, by the number of sets, The thickness of the SiOCN layer or SiOC layer formed per cycle) can be improved. This also improves the deposition rate (the thickness of the SiOCN film or the SiOC film formed per unit time).

When a SiOCN film having a predetermined composition or a SiOC film is formed, gas purge, inert gas replacement, atmospheric pressure return, boat unloading, and wafer discharge are performed in the same manner as the first sequence.

(Third sequence)

Next, the third sequence of the present embodiment will be described. Fig. 6 is a diagram showing an example of the film formation flow in the third sequence of the present embodiment. Fig. 9 is a diagram showing an example of timing of gas supply in the third sequence of the present embodiment. Fig. 9 (a) shows a sequence example in which film formation is performed without using plasma (in a non-plasma) And FIG. 9 (b) shows a sequence example in which film formation is performed using plasma.

In the third sequence of the present embodiment,

Forming a first layer containing silicon, nitrogen and carbon on the wafer 200 by alternately supplying the chlorosilane-based raw material and the aminosilane-based raw material to the wafer 200 in the treatment chamber 201;

A step of modifying the first layer by supplying an amine-based raw material to the wafer 200 in the treatment chamber 201 to form a silicon carbonitride layer as a second layer; And

A step of nitriding the second layer by supplying a nitrogen-containing gas (nitriding gas) activated by heat or plasma to the wafer 200 in the treatment chamber 201 to form a silicon carbonitride layer as a third layer;

A silicon nitride film of a predetermined composition and a predetermined film thickness is formed on the wafer 200 by performing a cycle a predetermined number of times.

Here, " alternately supplying the chlorosilane-based raw material and the aminosilane-based raw material " means that one of the raw materials of the chlorosilane-based raw material and the aminosilane-based raw material is supplied and then the other raw material is supplied, In this case, the set includes both the case of performing the set once and the case of repeating the set a plurality of times. That is, to perform this set one or more times (a predetermined number of times).

Further, the phrase " a cycle including the step of forming the first layer, the step of forming the second layer and the step of forming the third layer " is performed a predetermined number of times " When the step of forming the third layer and the step of forming the third layer are taken as one cycle, this includes both the case of performing this cycle once and the case of repeating this cycle a plurality of times. That is, this cycle is performed at least once (a predetermined number of times).

Figs. 6 and 9 show a case where a set composed of the above-described set, that is, the step of supplying one of the raw materials out of the chlorosilane-based raw material and the aminosilane-based raw material, and the subsequent step of supplying the other raw material, There is shown an example of a sequence in which the above-described cycle, that is, the process of forming the first layer, the process of forming the second layer, and the process of forming the third layer is performed a predetermined number of times.

That is, in the film formation sequence of Figs. 6 and 8,

A first layer containing silicon, nitrogen, and carbon is formed on the wafer 200 by supplying the chlorosilane-based raw material to the wafer 200 in the treatment chamber 201 and then supplying the aminosilane-based raw material to the wafer 200 in the treatment chamber 201 ;

A step of modifying the first layer by supplying an amine-based raw material to the wafer 200 in the treatment chamber 201 to form a silicon carbonitride layer as a second layer; And

A step of modifying the second layer by supplying heat or a plasma-activated nitrogen-containing gas to the wafer 200 in the treatment chamber 201 to form a silicon carbonitride layer as a third layer;

A silicon nitride film of a predetermined composition and a predetermined film thickness is formed on the wafer 200 by performing a cycle a predetermined number of times.

Hereinafter, the third sequence of the present embodiment will be described in detail. Here, the HCDS gas as the chlorosilane-based source gas, the 3DMAS gas as the aminosilane-based source gas, the TEA gas as the amine-based source gas, and the NH ₃ gas as the nitrogen-containing gas are used An example of forming a silicon carbide (SiCN) film as an insulating film on a substrate will be described.

Wafer charge, boat load, pressure adjustment, temperature adjustment, and wafer rotation are performed in the same manner as the first sequence. Thereafter, the following four steps are sequentially executed.

[Step 1]

Step 1 is performed in the same manner as Step 1 of the first sequence. That is, the processing conditions in step 1, reactions to be generated, layers to be formed, and the like are the same as those in step 1 in the first sequence. That is, in this step, the silicon-containing layer is formed on the wafer 200 by supplying the HCDS gas into the process chamber 201.

[Step 2]

Step 2 is performed in the same manner as step 2 of the first sequence. That is, the processing conditions in step 2, the reaction to be generated, the layer to be formed, and the like are the same as those in step 2 in the first sequence. That is, in this step, the silicon-containing layer and the 3DMAS gas are reacted by supplying the 3DMAS gas into the processing chamber 201 to form the first layer containing Si, N and C.

[Step 3]

Step 3 is performed in the same manner as step 3 of the first sequence. That is, the processing conditions in step 3, the reaction to be generated, the layer to be formed, and the like are the same as those in step 3 in the first sequence. That is, in this step, the first layer containing Si, N and C is reacted with the TEA gas by the supply of the TEA gas into the treatment chamber 201, so that the ratio of the C component is larger than that of the first layer, (SiCN layer) having a smaller impurity component than the first layer.

The pressure in the process chamber 201 when the TEA gas is supplied to the wafer 200 is set to be larger than the pressure in the process chamber 201 when the HCDS gas and the 3DMAS gas are supplied to the wafer 200 in steps 1 and 2 And it is preferable that the pressure in the processing chamber 201 when the NH ₃ gas is supplied to the wafer 200 in Step 4 to be described later is made larger. The pressure in the processing chamber 201 when NH ₃ gas is supplied to the wafer 200 in step 4 is set to be higher than the pressure in the processing chamber 201 when supplying HCDS gas and 3DMAS gas to the wafer 200 in steps 1 and 2 The pressure in the processing chamber 201 when the TEA gas is supplied to the wafer 200 is set to be higher than the pressure in the processing chamber 201 when the NH ₃ gas is supplied to the wafer 200 in Step 4 . The pressure in the processing chamber 201 when the HCDS gas and the 3DMAS gas are supplied to the wafer 200 is P ₁ and P ₂ [Pa], respectively, and the processing chamber 201 when the TEA gas is supplied to the wafer 200 P ₃ [Pa], and the pressure in the processing chamber 201 when NH ₃ gas is supplied to the wafer 200 is P ₄ [Pa], the pressure P ₁ to the pressure P _{4 are set} to P _3> preferably each set so as to satisfy the relation of P _1, P _2, and further more preferable that each set so as to satisfy the relationship of P _3> P _4, and also P _3> P _4> P _1, P < ₂ &_gt; are satisfied. That is, it is preferable that the pressure in the process chamber 201 when the TEA gas is supplied to the wafer 200 is the highest in steps 1 to 4.

The ratio of the C component in the second layer (SiCN layer) can be made larger than the ratio of the N component by setting the pressure in the processing chamber 201 at the time of supplying the TEA gas to such a pressure, and the C rich SiCN It becomes possible to form a layer. Thus, even after the second layer (SiCN layer) is nitrided in Step 4, it is possible to maintain the state where the ratio of the C component is larger than the ratio of the N component, and it becomes possible to form a SiCN layer with a high C concentration. That is, it becomes possible to form a SiCN film having a high C concentration.

[Step 4] (NH ₃ gas supply)

After the step 3 ends and removal of the residual gas in the process chamber 201, a fourth, open the valve (243d) of the gas supply pipe (232d), it sheds the NH ₃ gas in the fourth gas supply pipe (232d). The NH ₃ gas flowing in the fourth gas supply pipe 232d is regulated in flow rate by the mass flow controller 241d. The NH ₃ gas whose flow rate is adjusted is supplied into the buffer chamber 237 from the gas supply hole 250d of the fourth nozzle 249d. At this time, the NH ₃ gas supplied into the buffer chamber 237 is activated (excited) by heat without applying high frequency power between the first rod-shaped electrode 269 and the second rod-shaped electrode 270, Is supplied from the exhaust pipe 250e into the process chamber 201 and exhausted from the exhaust pipe 231 (see Fig. 9A). At this time, high-frequency power is applied between the first rod-shaped electrode 269 and the second rod-shaped electrode 270 from the high-frequency power source 273 through the matching unit 272, The supplied NH ₃ gas is activated (excited) by a plasma and supplied as active species from the gas supply hole 250e into the process chamber 201 and exhausted from the exhaust pipe 231 (see FIG. 9B). At this time, thermal or plasma-activated NH ₃ gas is supplied to the wafer 200. Simultaneously, the valve 243h is opened and N ₂ gas is flowed into the inert gas supply pipe 232h. The N ₂ gas is supplied into the processing chamber 201 together with the NH ₃ gas, and is exhausted from the exhaust pipe 231.

At this time, valves 243e, 243f and 243g are opened to prevent the inflow of O ₂ gas into the first nozzle 249a, the second nozzle 249b and the third nozzle 249c, and the first inert gas supply pipe N ₂ gas is passed through the second inert gas supply pipe 232f, the second inert gas supply pipe 232f and the third inert gas supply pipe 232g. The N ₂ gas is supplied through the first gas supply pipe 232a, the second gas supply pipe 232b, the third gas supply pipe 232c, the first nozzle 249a, the second nozzle 249b and the third nozzle 249c And is then exhausted from the exhaust pipe 231. [

When the NH ₃ gas is activated by heat without activation by plasma, the APC valve 244 is appropriately adjusted to set the pressure in the processing chamber 201 to a pressure within a range of, for example, 1 Pa to 3,000 Pa. The NH ₃ gas is thermally activated in the fourth nozzle 249d or in the buffer chamber 237 or in the processing chamber 201 by the non-plasma by setting the pressure in the processing chamber 201 to a relatively high pressure as described above It becomes possible. In addition, NH ₃ gas can be softly reacted by supplying heat by activating it, so that nitridation described later can be softly performed. When the NH ₃ gas is flowed as an active species (NH ₃ *), that is, a plasma excited species by activating the NH ₃ gas by plasma, the APC valve 244 is suitably adjusted to set the pressure in the treatment chamber 201 to a pressure within a range of 1 Pa to 100 Pa do. The supply flow rate of the NH ₃ gas controlled by the mass flow controller 241d is set to a flow rate within a range of, for example, 100 sccm to 10,000 sccm. The supply flow rates of the N ₂ gas to be controlled by the mass flow controllers 241h, 241e, 241f, and 241g are each set to a flow rate within a range of, for example, 100 sccm to 10,000 sccm. At this time, when NH ₃ gas is heated and activated, the partial pressure of the NH ₃ gas in the processing chamber 201 is set to a pressure within a range of, for example, 0.01 Pa to 2,970 Pa. When the NH ₃ gas is activated by plasma, the partial pressure of the NH ₃ gas in the processing chamber 201 is set to a pressure within a range of, for example, 0.01 to 99 Pa. Heat activated which NH ₃ gas, or the time of supplying to the wafer 200, the active species obtained by activating the NH ₃ gas into a plasma, i.e., the gas supply time (irradiation time), for example from 1 second to 120 seconds, preferably Is a time within a range of 1 second to 60 seconds. The temperature of the heater 207 at this time is set such that the temperature of the wafer 200 is, for example, 250 DEG C to 700 DEG C, preferably 300 DEG C to 650 DEG C, more preferably 350 DEG C to 600 DEG C Set the temperature to the temperature within the range. When NH ₃ gas is activated by plasma, the RF power applied between the first bar-shaped electrode 269 and the second bar-shaped electrode 270 from the RF power supply 273 is, for example, in the range of 50 W to 1,000 W .

At this time, the gas flowing into the processing chamber 201 is an active species obtained by activating thermally activated NH ₃ gas or NH ₃ gas by plasma by increasing the pressure in the processing chamber 201, Does not spill HCDS gas, 3DMAS gas or TEA gas. Therefore, the NH ₃ gas reacts with at least a part of the second layer (SiCN layer) formed on the wafer 200 in Step 3, without activating the vapor phase reaction and activating or activating the NH ₃ gas. Whereby the second layer is nitrided and reformed into a third layer. And the third layer becomes a silicon carbonitride layer (SiCN layer) having less N rich impurities than the second layer.

Further, as shown in Fig. 9A, the second layer is thermally nitrided by flowing NH ₃ gas into the processing chamber 201 with the activation of the heat, thereby modifying (changing) the SiCN layer with a small amount of impurities. At this time, the second layer is reformed into a SiCN layer having a low impurity while increasing the proportion of the N component in the second layer. At this time, the Si-N bonds in the second layer are increased by the energy of the nitriding species (the action of thermal nitrification by NH ₃ gas), while the Si-C bonds and the Si-Si bonds are decreased, The proportion of the C component and the proportion of the Si component in the film are decreased. In addition, impurities such as Cl remaining in the second layer due to the energy of the nitrifying species are eliminated and excluded as HCl or NH ₄ Cl or the like. That is, the second layer can be reformed into a SiCN layer having less impurities while changing the composition ratio in the direction of increasing the nitrogen concentration and decreasing the carbon concentration and the silicon concentration. At this time, the ratio of the N component in the SiCN layer, that is, the nitrogen concentration can be finely adjusted by controlling the processing conditions such as the pressure in the processing chamber 201 and the gas supply time, and the composition ratio of the SiCN layer can be more strictly controlled can do.

Further, as shown in FIG. 9 (b), the active layer obtained by activating the NH ₃ gas with plasma is caused to flow into the processing chamber 201, thereby plasma nitriding the second layer, thereby modifying the SiCN layer with a small amount of impurities ). At this time, the second layer is reformed into a SiCN layer having a low impurity while increasing the proportion of the N component in the second layer. At this time, the Si-N bonds in the second layer are increased by the nitriding species, that is, the energy of the plasma excitation species (action of plasma nitridation by NH ₃ gas), while the Si-C bonds and the Si- And the ratio of the C component and the Si component in the second layer decreases. Further, the impurities such as Cl remaining in the second layer due to the energy of the plasma excitation species are desorbed and excluded as HCl or NH ₄ Cl or the like. That is, the second layer can be reformed into a SiCN layer having less impurities while changing the composition ratio in the direction of increasing the nitrogen concentration and decreasing the carbon concentration and the silicon concentration. At this time, the ratio of the N component in the SiCN layer, that is, the nitrogen concentration can be finely adjusted by controlling the processing conditions such as the pressure in the processing chamber 201 and the gas supply time, and the composition ratio of the SiCN layer can be more strictly controlled can do.

At this time, it is preferable that the nitridation reaction of the second layer is not saturated. For example, in the case where the second layer having a thickness of several atomic layers is formed in Step 1 to Step 3, it is preferable to nitride a part of the second layer. In this case, the nitriding is performed under the condition that the nitridation reaction of the second layer becomes unsaturated so as not to nitride the entire second layer of the thickness of the atomic atom layer.

In order to make the nitridation reaction of the second layer unsaturated, the treatment conditions in Step 4 may be set to the above-described treatment conditions, and the nitridation reaction in the second layer may be unsaturated .

[When NH ₃ gas is heated and activated]

Wafer temperature: 500 ° C to 600 ° C

Pressure in the treatment chamber: 133 Pa to 2,666 Pa

NH ₃ gas partial pressure: 33 Pa to 2,515 Pa

NH ₃ gas supply flow rate: 1,000 sccm to 5,000 sccm

N ₂ gas supply flow rate: 300 sccm to 3,000 sccm

NH ₃ gas supply time: 6 to 60 seconds

[When NH ₃ gas is activated by plasma activation]

Wafer temperature: 500 ° C to 600 ° C

Pressure in the treatment chamber: 33 Pa to 80 Pa

NH ₃ gas partial pressure: 8 Pa to 75 Pa

NH ₃ gas supply flow rate: 1,000 sccm to 5,000 sccm

N ₂ gas supply flow rate: 300 sccm to 3,000 sccm

NH ₃ gas supply time: 6 to 60 seconds

(Removal of residual gas)

After the third layer is formed on the wafer 200, the valve 243d of the fourth gas supply pipe 232d is closed and the supply of the NH ₃ gas is stopped. At this time, the APC valve 244 of the exhaust pipe 231 is opened, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246 so as to be unreacted remaining in the processing chamber 201, NH ₃ gas or reaction by-products are excluded from the inside of the processing chamber 201. Further, the valves 243h, 243e, 243f, and 243g are kept in the open state to maintain the supply of the N ₂ gas as the inert gas into the processing chamber 201. The N ₂ gas acts as a purge gas, thereby enhancing the effect of eliminating NH ₃ gas or reaction by-products remaining in the processing chamber 201 after the unreacted reaction or the third layer formation, from the inside of the processing chamber 201 .

At this time, the gas remaining in the processing chamber 201 may not be entirely excluded, or the processing chamber 201 may not be completely purged. If there is a small amount of gas remaining in the processing chamber 201, no adverse effect occurs in step 1 performed thereafter. At this time, the flow rate of the N ₂ gas to be supplied into the processing chamber 201 is not limited to a large flow rate. For example, by supplying the same amount as the volume of the reaction tube 203 (processing chamber 201) It is possible to carry out purging to such an extent that adverse effects do not occur. By not completely purging the inside of the processing chamber 201, the purging time can be shortened and the throughput can be improved. In addition, it becomes possible to suppress the consumption of N ₂ gas to the minimum necessary.

Nitrogen-containing gas as the dia Zen (N ₂ H ₂₎ in addition to the activate the NH ₃ gas as a heat or plasma gas gas, hydrazine (N ₂ H ₄₎ gas, N ₃ a H ₈ gas, the activating gas with heat or plasma Or a gas obtained by diluting these gases with a rare gas such as Ar gas, He gas, Ne gas or Xe gas may be activated by heat or plasma.

(A predetermined number of times)

By performing the above-described steps 1 to 4 in one cycle and performing this cycle one or more times (a predetermined number of times), a silicon nitride film (SiCN film) of a predetermined composition and a predetermined film thickness can be formed on the wafer 200 . It is also preferable that the above cycle is repeated a plurality of times. That is, the SiCN layer formed per cycle is made smaller than the desired film thickness, and the cycle is repeated a plurality of times until a desired film thickness is obtained. The SiCN film may also be referred to as a thin film containing silicon (Si), carbon (C) and nitrogen (N).

Further, by performing the cycle including the step of alternately performing Step 1 and Step 2 described above a predetermined number of times, the step of performing Step 3, and the step of performing Step 4, A SiCN film having a predetermined composition and a predetermined film thickness may be formed. That is, the steps of performing the set number of times, performing the step 3, and performing the step 4 in one set of the steps 1 and 2 described above are performed one cycle, and the cycle is performed a predetermined number of times , A SiCN film having a predetermined film thickness may be formed on the wafer 200.

By carrying out this cycle a predetermined number of times with one cycle of performing the set number of times, performing the step 3, and performing the step 4 with one set of the steps 1 and 2 described above, The controllability of the composition ratio of the SiCN film can be improved. The absolute amount of the silicon component, the nitrogen component and the carbon component of the first layer can be increased or decreased by increasing or decreasing the number of sets constituted in steps 1 and 2. In this way, By modifying in steps 3 and 4, the ratio of each component of the SiCN layer can be adjusted by the number of sets, and the ratio of each component of the finally formed SiCN film can be controlled by the number of sets.

Further, by increasing the number of sets constituted in steps 1 and 2, it is possible to increase the number of layers of the first layer formed per cycle, that is, the thickness of the first layer formed per cycle, by the number of sets, The thickness of the SiCN layer formed per cycle) can be improved. In this way, the film-forming rate (film thickness of the SiCN film formed per unit time) can be improved.

In addition, by performing this cycle a predetermined number of times with one cycle of the step of performing this set a predetermined number of times and the step of performing the step 4 by using the above-described steps 1 to 3 as one set, A SiCN film having a film thickness may be formed.

The control of the composition ratio of the SiCN film can be improved by performing this cycle a predetermined number of times with one cycle of the step of performing the set number of times and the step of performing step 4 with the steps 1 to 3 described above being one set, . The absolute amount of the silicon component, the nitrogen component and the carbon component of the second layer can be increased or decreased by increasing or decreasing the number of sets constituted by the steps 1 to 3. In this way, By modifying in step 4, the ratio of each component of the SiCN layer can be adjusted by the number of sets, and the ratio of each component of the finally formed SiCN film can be controlled by the number of sets.

Further, by increasing the number of sets constituted in steps 1 to 3, it is possible to increase the number of layers of the second layer formed per cycle, i.e., the thickness of the second layer formed per cycle, by the number of sets, The thickness of the SiCN layer formed per unit cycle) can be improved. In this way, the film-forming rate (film thickness of the SiCN film formed per unit time) can be improved.

When a film forming process for forming a SiCN film having a predetermined film thickness with a predetermined composition is performed, gas purging, inert gas substitution, atmospheric pressure return, boat unloading, and wafer discharge are performed in the same manner as the first sequence.

According to this embodiment, when an insulating film is formed using a chlorosilane-based raw material or an aminosilane-based raw material, a silicon insulating film of a desired composition having a high silicon density in a low temperature region can be formed. In addition, a silicon insulating film having an ideal stoichiometric ratio can be formed. Further, according to an experiment conducted by the inventors, it has been difficult to deposit silicon on a wafer at a deposition rate that satisfies the production efficiency at a temperature range of 500 ° C or lower when a chlorosilane-based raw material is used. In the case of using an aminosilane-based raw material group, deposition of silicon on a wafer was not confirmed at a temperature range of 500 DEG C or lower. However, according to the technique of the present embodiment, it is possible to form a silicon insulating film of good quality at a deposition rate that satisfies the production efficiency even in a low temperature region of 500 DEG C or less.

When the film forming temperature is lowered, the kinetic energy of the molecules is usually lowered, so that the chlorine contained in the chlorosilane-based raw material or the amines contained in the aminosilane-based raw material are less likely to react and desorb, Remains on the surface. The residual ligands of these residual ligands cause steric hindrance (disorder), which inhibits the adsorption of silicon onto the surface of the wafer, resulting in a decrease in silicon density and deterioration of the film. However, by reacting the two silane sources, that is, the chlorosilane-based raw material and the aminosilane-based raw material appropriately under such a condition that such reaction and desorption can not proceed, it is possible to desorb the remaining ligand. The steric hindrance is eliminated by the desorption of the residual ligand, whereby the silicon can be adsorbed to the opened site, and the silicon density can be increased. Thus, it is considered that a film having a high silicon density can be formed even at a low temperature region of 500 DEG C or less.

According to this embodiment, after the first layer containing Si, N and C, that is, the silicon insulating layer is formed on the wafer by supplying the chlorosilane-based raw material and then supplying the aminosilane-based raw material, Since the amine base material is supplied, the nitrogen concentration or the carbon concentration of the silicon insulating layer can be appropriately adjusted, and the silicon insulating film having the desired characteristics can be formed while controlling the composition ratio.

According to this embodiment, a chlorosilane-based raw material is supplied, and thereafter, an aminosilane-based raw material is supplied to form a first layer containing Si, N and C, that is, a silicon insulating layer on the wafer, The nitrogen concentration, the carbon concentration, or the oxygen concentration of the silicon insulating layer can be appropriately adjusted because the base material is supplied and then the oxidizing gas or the nitriding gas is supplied. Can be formed.

According to this embodiment, the pressure in the process chamber when supplying the amine-based raw material can be made larger than the pressure in the process chamber when supplying the chlorosilane-based raw material, the aminosilane-based raw material, and the reaction gas. The pressure in the process chamber when supplying the reaction gas is made larger than the pressure in the process chamber when the chlorosilane-based material and the aminosilane-based material are supplied, and the pressure in the process chamber when supplying the amine- Can be made larger than the pressure. By adjusting the pressure in the treatment chamber as described above, it becomes possible to form a C-rich second layer (SiCN layer). As a result, even after the second layer (SiCN layer) is oxidized or nitrided, it is possible to maintain a state where the ratio of the C component is larger than that of the N component, and it is possible to form a SiOCN film, SiOC film or SiCN film with a high C concentration It becomes.

According to the present embodiment, it is also possible to perform this cycle a predetermined number of times by setting the steps 1 and 2 as one set, performing this set a predetermined number of times, and performing the step 3 as one cycle 1 sequence). It is also possible to perform this cycle a predetermined number of times with one cycle of performing this set a predetermined number of times, performing the step 3, and performing the step 4 with one set of steps 1 and 2 as one set Second, and third sequences). Also, it is also possible to perform this cycle a predetermined number of times (steps 2 and 3), with the steps of performing this set a predetermined number of times in steps 1 to 3 and performing the step 4 in one cycle. The nitrogen concentration, the carbon concentration, or the oxygen concentration in the silicon insulating film (SiOCN film, SiOC film or SiCN film) can be appropriately adjusted by performing the film formation in this sequence, and the controllability of the composition ratio of the silicon insulating film can be improved have. Further, the cycle rate can be improved and the film formation rate can be improved. It is also possible to form a silicon insulating film having a different composition ratio in the film thickness direction by changing the number of sets per cycle. The carbon concentration or the oxygen concentration in the film thickness direction (depth direction) may be gradually lowered in the film thickness direction (depth direction) or the silicon insulating film having the composition such that the oxygen concentration can be gradually increased in the film thickness direction It is also possible to form a silicon insulating film having a composition as shown in Fig.

Further, by using the silicon insulating film formed by the technique of this embodiment as a sidewall spacer, it becomes possible to provide a device forming technique with a small leakage current and excellent processability.

Further, by using the silicon insulating film formed by the technique of the present embodiment as an etching stopper, it becomes possible to provide a device forming technique with excellent processability.

According to the present embodiment, a silicon insulating film having an ideal stoichiometric ratio can be formed without using plasma even at a low temperature region. Further, since a silicon insulating film can be formed without using a plasma, it is possible to adapt to a process of worrying about plasma damage, such as a SADP film of DPT.

Further, in the above-described embodiment, when the first layer containing Si, N and C is formed in each sequence, the chlorosilane-based raw material is supplied to the wafer 200 in the processing chamber 201, The method of feeding the raw material may be reversed. That is, the aminosilane-based raw material may be supplied, and then the chlorosilane-based raw material may be supplied. That is, one of the chlorosilane-based raw material and the aminosilane-based raw material is supplied, and then the other raw material is supplied. Further, the step of supplying one of the raw materials of the chlorosilane-based raw material and the aminosilane-based raw material and the step of supplying the other raw material may be alternately performed a predetermined number of times. It is also possible to change the film quality and the composition ratio of the thin film formed in each sequence by changing the order of flowing the raw materials.

It is also possible to change the film quality and the composition ratio of the thin film formed in each sequence by changing the order of flowing the chlorosilane-based raw material and the aminosilane-based raw material, as well as the order of flowing all the gases including the chlorosilane- It is possible.

In the above-described embodiments, examples in which chlorosilane-based raw materials and aminosilane-based raw materials are used in forming the first layer containing Si, N and C in each sequence have been described. However, instead of the chlorosilane- A silane-based raw material having a halogen-based ligand other than the raw material may be used. For example, instead of the chlorosilane-based raw material, a fluorosilane-based raw material may be used. Here, the fluorosilane-based raw material is a silane-based raw material containing a fluoro group and is a raw material containing at least silicon (Si) and fluorine (F). As the fluorosilane-based source gas, silicon fluoride gas such as silicon tetrafluoride (SiF ₄ ) gas or silicon hexafluoride (Si ₂ F ₆ ) gas can be used. In this case, when the first layer containing Si, N and C is formed in each sequence, the fluorosilane-based raw material is supplied to the wafer 200 in the process chamber 201, and then the aminosilane-based raw material is supplied Or the aminosilane-based raw material is supplied, and then the fluorosilane-based raw material is supplied or alternatively, these are carried out alternately a predetermined number of times.

Further, in the above-described embodiment, an example of using plasma in step 4 of the third sequence has been described, but plasma may be used in each step of another sequence. For example, each layer may be reformed by plasma nitridation (nitrogen doping), plasma carbonization (carbon doping), or plasma oxidation (oxygen doping) by activating and supplying each gas with plasma in each step of each sequence. However, it is preferable that the use of the plasma is not suitable for the process in which the plasma damage is concerned, and is applied to the process in which there is no possibility of other plasma damage.

Further, in the step of supplying the oxygen-containing gas, a hydrogen-containing gas (reducing gas) may be supplied together with the oxygen-containing gas. Containing gas and a hydrogen-containing gas are supplied into the processing chamber 201 under an atmospheric pressure (reduced pressure) atmosphere, the oxygen-containing gas and the hydrogen-containing gas react with each other in the processing chamber 201 to form atomic oxygen atomicoxygen, O) oxide paper is produced containing oxygen of H ₂ O-free, such as, it can be oxidized to each layer by the oxidizing species. In this case, oxidation can be performed at a higher oxidizing power than by oxidizing the oxygen-containing gas alone. This oxidation process is performed in a reduced-pressure atmosphere of a non-plasma. As the hydrogen-containing gas (reducing gas), for example, hydrogen (H ₂ ) gas or deuterium (D ₂ ) gas can be used.

Further, in the above-described embodiment, when the first layer containing Si, N and C is formed in each sequence, the chlorosilane-based raw material is supplied to the wafer 200 in the processing chamber 201, The CVD reaction may be generated by supplying the chlorosilane-based raw material and the aminosilane-based raw material simultaneously to the wafer 200 in the process chamber 201. The processing conditions in this case may be similar to the processing conditions in the respective sequences of the above-described embodiment. Similar effects to those of the above-described embodiment can be obtained even if the chlorosilane-based raw material and the aminosilane-based raw material are simultaneously supplied to the wafer 200 in the treatment chamber 201 without supplying them sequentially. However, it is preferable to sequentially supply the respective raw materials, that is, to supply the chlorosilane-based raw material and the aminosilane-based raw material alternately through the purge in the treatment chamber 201, as in the above- The aminosilane-based raw material can be appropriately reacted under the condition that the surface reaction is dominant and the controllability of the film thickness control can be improved.

In the embodiment described above, an example in which one type of thin film (short film) is formed on the wafer at one time in the processing chamber in each sequence has been described. However, by appropriately combining each of the sequences described above, A laminated film of two or more kinds of thin films can be formed at one time. For example, the sequence of FIG. 4 and the sequence of FIG. 5 may be alternately performed in-situ in the process chamber to form a laminated film in which SiCN films and SiOCN films or SiOC films are alternately laminated . In addition, for example, the SiOCN film or the laminated film in which the SiOC film and the SiCN film are alternately laminated can be formed by carrying out in-situ alternation between the sequence of FIG. 5 and the sequence of FIG. 6 in the treatment chamber.

As described above, the present invention can be preferably applied not only to a monolayer but also to a laminated film. In this case, the same operational effects as those of the above-described embodiment can be obtained.

The present invention is not limited to the case where a silicon-based insulating film containing silicon as a semiconductor element is formed as a thin film in the above-described embodiment. However, the present invention is not limited to this. (Al), molybdenum (Mo), and the like can be formed.

For example, the present invention can be applied to the case of forming a Ti-based thin film in which a titanium nitride film (TiCN film), a titanium oxynitride film (TiOCN film), a titanic acid film (TiOC film) have.

For example, the present invention can also be applied to a case of forming a Zr-based thin film in which a zirconium carbonitride film (ZrCN film), a zirconium oxyanitride film (ZrOCN film), a zirconium oxalate film (ZrOC film) .

For example, the present invention can also be applied to the case of forming a hafnium carbonitride film (HfCN film), a hafnium oxyanitride nitride film (HfOCN film), a hafnium oxalate film (HfOC film), a Hf system thin film obtained by combining or mixing them, .

For example, the present invention can also be applied to the case of forming a Ta-based thin film in which a tantalum carbonitride film (TaCN film), a tantalum oxy-nitride film (TaOCN film), a tantalum oxalate film (TaOC film) .

For example, the present invention can also be applied to the case of forming an aluminum-based thin film (AlCN film), an aluminum oxynitride film (AlOCN film), an aluminum oxynitride film (AlOC film) .

For example, the present invention can also be applied to the case of forming a Mo-based thin film in which a molybdenum carbonitride film (MoCN film), a molybdenum oxynitride film (MoOCN film), a molybdenum oxynitride film (MoOC film) .

In this case, a raw material (first raw material) containing a metal element and a chloro group is used in place of the chlorosilane-based raw material in the above-described embodiment, and a raw material containing a metal element and an amino group ), The film formation can be performed by the same sequence as in the above-described embodiment.

For example, when the first sequence of the above-described embodiment is applied to the formation of the metal-based thin film,

The first raw material including the metal element and the chloro group and the second raw material including the metal element and the amino group are alternately supplied to the wafer 200 in the treatment chamber 201, , A first layer comprising nitrogen and carbon; And

A step of modifying the first layer by supplying an amine-based raw material to the wafer 200 in the treatment chamber 201 to form a metal carbonitride layer as a second layer;

Is performed alternately a predetermined number of times to form a metal carbonitride film having a predetermined composition and a predetermined film thickness on the wafer 200.

Further, when the second sequence of the above-described embodiment is applied to the formation of the metal-based thin film,

The first raw material including the metal element and the chloro group and the second raw material including the metal element and the amino group are alternately supplied to the wafer 200 in the treatment chamber 201, , A first layer comprising nitrogen and carbon;

A step of modifying the first layer by supplying an amine-based raw material to the wafer 200 in the treatment chamber 201 to form a metal carbonitride layer as a second layer; And

Oxidizing the second layer by supplying heat-activated oxygen-containing gas (oxidizing gas) to the wafer 200 in the processing chamber 201 to form a metal oxynitride layer or metal oxynitride layer as a third layer;

Is performed a predetermined number of times to form a metal oxynitride film or metal oxynitride film having a predetermined composition and a predetermined film thickness on the wafer 200. [

Further, when the third sequence of the above-described embodiment is applied to the formation of the metal-based thin film,

The first raw material including the metal element and the chloro group and the second raw material including the metal element and the amino group are alternately supplied to the wafer 200 in the treatment chamber 201, , A first layer comprising nitrogen and carbon;

A step of modifying the first layer by supplying an amine-based raw material to the wafer 200 in the treatment chamber 201 to form a metal carbonitride layer as a second layer; And

A step of nitriding the second layer by supplying a nitrogen-containing gas (nitriding gas) activated by heat or plasma to the wafer 200 in the treatment chamber 201 to form a metal carbonitride layer as a third layer;

To form a metal nitride film having a predetermined composition and a predetermined film thickness on the wafer 200 by performing a cycle a predetermined number of times.

In any case, " alternately feeding a first raw material containing a metal element and a chloro group and a second raw material containing a metal element and an amino group " means that the first raw material containing a metal element and a chloro group, Is supplied to the wafer 200 in the processing chamber 201. Thereafter, the other raw material, which is different from one of the raw materials of the first raw material and the second raw material, is supplied to the processing chamber 201, When the set is supplied to the wafer 200 within the set, the set includes both the case of performing the set once and the case of repeating the set a plurality of times. That is, to perform this set one or more times (a predetermined number of times).

For example, when a Ti-based thin film is formed as a metal thin film, a raw material containing Ti and a chloro group such as titanium tetrachloride (TiCl ₄ ) is used as a first raw material and tetrakisethylmethylaminotitanium (Ti [N (C ₂ H ₅ ) (CH ₃ )] ₄ , abbreviated as TEMAT), tetrakis dimethylaminotitanium (Ti [N (CH ₃ ) ₂ ] ₄ , abbreviated as TDMAT), tetrakis diethylaminotitanium (C ₂ H ₅ ) ₂ ] ₄ , abbreviation: TDEAT), and the like. As the amine-based raw material, the oxygen-containing gas, or the nitrogen-containing gas, the same gas as in the above-described embodiment can be used. The processing conditions at this time can be, for example, the same processing conditions as those of the above-described embodiment.

When a Zr based thin film is formed, for example, as a metal thin film, a raw material containing Zr and a chloro group such as zirconium tetrachloride (ZrCl ₄ ) is used as a first raw material, tetrakisethyl methylaminozirconium (Zr [ N (C ₂ H ₅ ) (CH ₃ )] ₄ , abbreviated as TEMAZ), tetrakis dimethylaminozirconium (Zr [N (CH ₃ ) ₂ ] ₄ , abbreviation TDMAZ), tetrakis diethylaminozirconium N (C ₂ H ₅ ) ₂ ] ₄ , abbreviation: TDEAZ), and the like. As the amine-based raw material, the oxygen-containing gas, or the nitrogen-containing gas, the same gas as in the above-described embodiment can be used. The processing conditions at this time can be, for example, the same processing conditions as those of the above-described embodiment.

In the case of forming a Hf-based thin film as a metal thin film, for example, a raw material containing Hf and chloro groups such as hafnium tetrachloride (HfCl ₄ ) is used as a first raw material and tetrakisethylmethylamino hafnium (Hf [ N (C ₂ H ₅ ) (CH ₃ )] ₄ , abbreviated as TEMAH), tetrakis dimethylamino hafnium (Hf [N (CH ₃ ) ₂ ] ₄ , abbreviation: TDMAH), tetrakis diethylamino hafnium N (C ₂ H ₅ ) ₂ ] ₄ , abbreviation: TDEAH), and the like. As the amine-based raw material, the oxygen-containing gas, or the nitrogen-containing gas, the same gas as in the above-described embodiment can be used. The processing conditions at this time can be, for example, the same processing conditions as those of the above-described embodiment.

As described above, the present invention can be applied not only to a silicon-based thin film but also to a metal-based thin film. In this case, the same effects as those of the above-described embodiment can be obtained.

That is, the present invention can be applied to a case where a thin film containing a predetermined element such as a semiconductor element or a metal element is formed.

In the above-described embodiment, an example has been described in which a film is formed using a batch type substrate processing apparatus that processes a plurality of substrates at one time. However, the present invention is not limited to this, The present invention can be suitably applied to a case of forming a film by using a single wafer type substrate processing apparatus for processing several substrates.

In addition, each of the above-described embodiments, each film formation sequence, each modification example, each application example, and the like can be appropriately combined and used.

The present invention can also be realized by, for example, changing the process recipe of an existing substrate processing apparatus. In the case of changing the process recipe, the process recipe according to the present invention may be installed in an existing substrate processing apparatus through an electric communication line or a recording medium on which the process recipe is recorded, or by operating an input / output apparatus of an existing substrate processing apparatus, It is also possible to change the process recipe itself to the process recipe according to the present invention.

Hereinafter, preferred embodiments of the present invention will be attached.

(Annex 1)

According to one aspect of the present invention,

A step of supplying a first source gas containing a predetermined element and a halogen group to a substrate in a treatment chamber and a step of supplying a second source gas containing the predetermined element and an amino group to the substrate in the treatment chamber are alternately performed a predetermined number of times Thereby forming a first layer containing the predetermined element, nitrogen and carbon on the substrate;

A step of modifying the first layer to form a second layer by supplying an amine-based source gas to the substrate in the treatment chamber; And

A step of forming a third layer by modifying the second layer by supplying a reaction gas different from the respective raw material gases to the substrate in the processing chamber;

A step of forming a thin film of a predetermined composition including the predetermined element on the substrate by performing a cycle a predetermined number of times.

Here, " the step of supplying the first source gas and the step of supplying the second source gas are alternately performed a predetermined number of times " is a step of supplying one of the source gases out of the first source gas and the second source gas, Thereafter, in the case where one set of the steps of supplying the other raw material gas different from the above-mentioned raw material gas in the first raw material gas and the second raw material gas is set as one set, And repeat both times. That is, to perform this set one or more times (a predetermined number of times).

The phrase " a cycle including the step of forming the first layer, the step of forming the second layer, and the step of forming the third layer " is performed a predetermined number of times " And the case of repeating a plurality of times. That is, this cycle is performed at least once (a predetermined number of times).

In this specification, similar expressions are used in the same sense.

(Annex 2)

The method for manufacturing a semiconductor device according to note 1,

The pressure in the processing chamber when supplying the amine-based source gas is made larger than the pressure in the processing chamber when the first source gas, the second source gas, and the reactive gas are supplied.

(Annex 3)

A manufacturing method of a semiconductor device according to note 2,

The pressure in the processing chamber when supplying the amine-based source gas is made larger than the pressure in the processing chamber when supplying the reaction gas, and the pressure in the processing chamber when the reactive gas is supplied is set to be higher than the pressure in the processing chamber when supplying the amine- Is made larger than the pressure in the treatment chamber when supplying the raw material gas.

(Note 4)

A manufacturing method of a semiconductor device according to note 3,

Wherein in the step of forming the third layer, an oxynitride gas is supplied as the reactive gas to the substrate to form a third layer,

In the step of forming the thin film, a silicon oxynitride film or a carbonized film is formed as the thin film.

(Note 5)

A manufacturing method of a semiconductor device according to note 3,

In the step of forming the third layer, the carbonitride layer is formed as the third layer by supplying a nitriding gas as the reactive gas to the substrate,

In the step of forming the thin film, a carbon nitride film is formed as the thin film.

(Note 6)

According to another aspect of the present invention,

A step of supplying a first source gas containing a predetermined element and a halogen group to a substrate in a treatment chamber and a step of supplying a second source gas containing the predetermined element and an amino group to the substrate in the treatment chamber are alternately performed a predetermined number of times Thereby forming a first layer containing the predetermined element, nitrogen and carbon on the substrate;

A step of modifying the first layer to form a second layer by supplying an amine-based source gas to the substrate in the treatment chamber; And

A step of forming a third layer by modifying the second layer by supplying a reaction gas different from the respective raw material gases to the substrate in the processing chamber;

A step of forming a thin film of a predetermined composition including the predetermined element on the substrate by performing a cycle a predetermined number of times.

(Note 7)

According to another aspect of the present invention,

A processing chamber for accommodating a substrate;

A first raw material gas supply system for supplying a first raw material gas containing a predetermined element and a halogen group to the substrate in the treatment chamber;

A second source gas supply system for supplying a second source gas containing the predetermined element and the amino group to the substrate in the treatment chamber;

A third source gas supply system for supplying an amine-based source gas to the substrate in the treatment chamber;

A reaction gas supply system for supplying a reaction gas different from the respective source gases to the substrate in the processing chamber; And

A process for supplying the first source gas to the substrate in the treatment chamber and a process for supplying the second source gas to the substrate in the treatment chamber are alternately performed a predetermined number of times, A process of forming a first layer containing nitrogen and carbon, a process of forming the second layer by modifying the first layer by supplying the amine-based source gas to the substrate in the process chamber, And a process of reforming the second layer by supplying the reaction gas to the substrate to form a third layer, so that a predetermined number of cycles of the process are performed on the substrate, The first source gas supply system, the second source gas supply system, the third source gas supply system, and the reaction gas supply system are controlled so as to form a thin film A controller;

And a substrate processing apparatus.

(Annex 8)

According to another aspect of the present invention,

A step of supplying a first raw material gas containing a predetermined element and a halogen group to a substrate in a processing chamber of the substrate processing apparatus and a step of supplying a second raw material gas containing the predetermined element and an amino group to the substrate in the processing chamber, A step of forming a first layer containing the predetermined element, nitrogen and carbon on the substrate by performing a predetermined number of times;

A step of forming the second layer by modifying the first layer by supplying an amine-based source gas to the substrate in the treatment chamber; And

A step of forming a third layer by modifying the second layer by supplying a reaction gas different from the respective source gases to the substrate in the treatment chamber;

A predetermined number of times to perform a cycle including the predetermined element to form a thin film having a predetermined composition including the predetermined element on the substrate.

(Note 9)

According to another aspect of the present invention,

A step of supplying a first raw material gas containing a predetermined element and a halogen group to a substrate in a processing chamber of the substrate processing apparatus and a step of supplying a second raw material gas containing the predetermined element and an amino group to the substrate in the processing chamber, A step of forming a first layer containing the predetermined element, nitrogen and carbon on the substrate by performing a predetermined number of times;

A step of forming the second layer by modifying the first layer by supplying an amine-based source gas to the substrate in the treatment chamber; And

A step of forming a third layer by modifying the second layer by supplying a reaction gas different from the respective source gases to the substrate in the treatment chamber;

There is provided a computer-readable recording medium recording a program that causes a computer to execute a procedure of forming a thin film of a predetermined composition including the predetermined element on a substrate by performing a cycle a predetermined number of times.

121: controller 200: wafer
201: processing chamber 202: processing path
203: reaction tube 207: heater
231: exhaust pipe 232a: first gas supply pipe
232b: second gas supply pipe 232c: third gas supply pipe
232d: fourth gas supply pipe 232j: fifth gas supply pipe

Claims (9)

A step of supplying a first source gas containing a predetermined element and a halogen group to a substrate in a treatment chamber and a step of supplying a second source gas containing the predetermined element and an amino group to the substrate in the treatment chamber are alternately performed a predetermined number of times Thereby forming a first layer containing the predetermined element, nitrogen and carbon on the substrate;
The pressure in the processing chamber is made larger than the pressure in the processing chamber when the first source gas, the second source gas, and the reaction gas are supplied, and an amine source gas containing carbon, nitrogen, and hydrogen is introduced into the processing chamber The first layer is modified to form a second layer containing a higher proportion of nitrogen than the proportion of nitrogen contained in the first layer and a higher proportion of carbon than the proportion of carbon contained in the first layer ; And
Forming a third layer by modifying the second layer by supplying the reaction gas different from each of the source gases to the substrate in the processing chamber;
And forming a thin film having a predetermined composition including the predetermined element on the substrate by performing a cycle a predetermined number of times. delete 2. The method according to claim 1, wherein the pressure in the processing chamber when supplying the amine-based source gas is larger than the pressure in the processing chamber when supplying the reaction gas, and the pressure in the processing chamber when supplying the reaction gas, Gas and the pressure in the processing chamber when supplying the second raw material gas. 4. The method according to claim 3, wherein in the step of forming the third layer, one of the oxynitride layer and the oxynitride layer is formed as the third layer by supplying an oxidizing gas as the reactive gas to the substrate,
Wherein in the step of forming the thin film, one of the oxynitride film and the oxynitride film is formed as the thin film. The method according to claim 3, wherein in the step of forming the third layer, a carbonitride layer is formed as the third layer by supplying a nitriding gas as the reactive gas to the substrate,
Wherein the step of forming the thin film forms a carbon nitride film as the thin film. A step of supplying a first source gas containing a predetermined element and a halogen group to a substrate in a treatment chamber and a step of supplying a second source gas containing the predetermined element and an amino group to the substrate in the treatment chamber are alternately performed a predetermined number of times Thereby forming a first layer containing the predetermined element, nitrogen and carbon on the substrate;
The pressure in the processing chamber is made larger than the pressure in the processing chamber when the first source gas, the second source gas, and the reaction gas are supplied, and an amine source gas containing carbon, nitrogen, and hydrogen is introduced into the processing chamber The first layer is modified to form a second layer containing a higher proportion of nitrogen than the proportion of nitrogen contained in the first layer and a higher proportion of carbon than the proportion of carbon contained in the first layer ; And
Forming a third layer by modifying the second layer by supplying the reaction gas different from each of the source gases to the substrate in the processing chamber;
And forming a thin film having a predetermined composition including the predetermined element on the substrate by performing a cycle a predetermined number of times. A processing chamber for accommodating a substrate;
A first source gas supply system for supplying a first source gas containing a predetermined element and a halogen group to the substrate in the treatment chamber;
A second source gas supply system for supplying a second source gas containing the predetermined element and the amino group to the substrate in the treatment chamber;
A third source gas supply system for supplying an amine-based source gas containing carbon, nitrogen and hydrogen to the substrate in the treatment chamber;
A reaction gas supply system for supplying a reaction gas different from each of the source gases to the substrate in the processing chamber; And
A process for supplying the first source gas to the substrate in the process chamber and a process for supplying the second source gas to the substrate in the process chamber are alternately performed a predetermined number of times to form the predetermined element, And forming a first layer containing carbon on the surface of the substrate in the process chamber; and a process of forming a first layer containing carbon and a pressure in the process chamber, wherein the pressure in the process chamber is larger than the pressure in the process chamber when supplying the first source gas, the second source gas, The first layer is modified to supply the amine-based source gas to a portion of the first layer in which the ratio of nitrogen to nitrogen contained in the first layer is higher than that of nitrogen contained in the first layer, Forming a second layer including the second layer on the substrate, and supplying the reaction gas to the substrate in the processing chamber to modify the second layer And forming a thin film of a predetermined composition including the predetermined element on the substrate by performing a cycle including a process of forming a third layer by a predetermined number of times, A control unit for controlling the supply system, the third source gas supply system, and the reaction gas supply system;
And the substrate processing apparatus. A step of supplying a first raw material gas containing a predetermined element and a halogen group to a substrate in a processing chamber of the substrate processing apparatus and a step of supplying a second raw material gas containing the predetermined element and an amino group to the substrate in the processing chamber, A step of forming a first layer containing the predetermined element, nitrogen and carbon on the substrate by performing a predetermined number of times;
The pressure in the processing chamber is made larger than the pressure in the processing chamber when the first source gas, the second source gas, and the reaction gas are supplied, and an amine source gas containing carbon, nitrogen, and hydrogen is introduced into the processing chamber The first layer is modified to form a second layer containing a higher proportion of nitrogen than the proportion of nitrogen contained in the first layer and a higher proportion of carbon than the proportion of carbon contained in the first layer Order; And
Forming a third layer by modifying the second layer by supplying the reaction gas different from each of the source gases to the substrate in the processing chamber;
Wherein the step of forming the thin film comprises the steps of: forming a thin film having a predetermined composition including the predetermined element on the substrate by performing a cycle a predetermined number of times. The manufacturing method of a semiconductor device according to claim 1, wherein the second layer includes the predetermined element, the nitrogen and the carbon, and the ratio of carbon is larger than the ratio of nitrogen.

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